KR19990064042A - Branched block ethylene polymer, preparation method thereof and composition comprising same - Google Patents

Abstract

Branched block ethylene polymers prepared from narrow ethylene polymers, ethylenically unsaturated functionalized organic compounds and reactive thermoplastic polymers and methods for their preparation are useful for preparing impact modified ethylene polymers.

Description

Branched block ethylene polymer, method for preparing the same, and composition comprising same

Field of invention

The present invention relates to ethylene polymers, more particularly to block polymers of ethylene polymers, compositions containing block ethylene polymers, and to methods for producing block ethylene polymers and compositions containing them.

Background technology

Methods for graft-modification of ethylene polymers with various olefinically unsaturated monomers are well known in the art. This modification method essentially makes the nonpolar polymer material miscible with the polar material at least to some extent.

However, the graft modification method can adversely affect one or more other properties of the ethylene polymer. For example, US Pat. Nos. 4,134,927, 3,884,882 and 5,140,074 all report undesirable changes in rheological properties due to crosslinking of graft modified materials. These changes ultimately affect the processability of the material and thus its usefulness in commercial use.

In addition, where it is desirable to mix the ethylene polymer with other molding polymers, graft modification of the ethylene polymer, which may be useful in terms of adhesion, can adversely affect the miscibility of the ethylene polymer with the mixing or molding polymer. . Thus, ethylene polymers can be modified to such an extent that they improve other properties of the ethylene polymer (and preferably the resulting mixture), such as the rheology thereof, without adversely affecting its miscibility with other polymers in the mixture. It is preferable.

A further particular problem facing the industry is the improvement of the properties of polycarbonates. This drawback has been alleviated to some extent by mixing polycarbonates with various olefin polymers (eg low density polyethylene or linear low density polyethylene) or thermoplastic rubbers (eg ethylene / propylene copolymers). These additive materials can improve the polycarbonate's resistance to solvents, but they tend to delaminate and cause offset reductions in the stiffness, impact resistance and weld strength of the mixed polycarbonate composition. This delamination and the resulting loss of usefulness are reported, for example, in US Pat. No. 4,496,693.

Impact resistance of polycarbonates can be improved by incorporation of emulsions or core-shell elastomers such as methacrylate / butadiene / styrene copolymers or butyl acrylate rubbers. However, these core-shell rubbers interfere with the processability of the mixture by increasing the viscosity and do not improve the solvent resistance of the polycarbonate. Thus, modifiers, especially olefin-based modifiers, which are mixed with thermoplastics (e.g. polycarbonates) to improve solvent resistance do not have a detrimental effect on stiffness, impact strength and weld strength, It is preferable when the same peeling is not caused.

U. S. Patent No. 5,346, 963 describes ethylene polymers grafted with ethylenically unsaturated compounds and mixtures of miscible thermoplastics and grafted ethylene polymers. However, the description of graft modified ethylene polymers in this document does not refer to branched block ethylene polymers as defined herein.

U.S. Patent 5,300,574 describes that if the grafting reaction is carried out in the presence of polyamide, crosslinking is reduced when maleic anhydride is grafted with saturated ethylene polymer. However, this patent does not mention branched block ethylene polymers.

U.S. Patent No. 5,346,963 to Hughes et al. Grafts with filled admixtures for polymers and one or more unsaturated organic compounds containing both ethylenically unsaturated and carbonyl groups in thermoplastic resin mixtures as impact modifiers for other polyolefins and polyamides. Substantially linear polyethylene is described.

One object of the present invention is to improve viscoelastic behavior and, when used as a modifier in a mixture with a thermoplastic molding polymer, improved rheological behavior in the mixture, good impact resistance, thin cross section and transparency of the film, surface hardness and reduced It is to prepare an ethylene-based polymer that gives notch sensitivity. This and other objects described below are obtained by the preparation of branched block ethylene polymers and the use of said branched block ethylene polymers in the compositions of the invention.

Summary of the Invention

In one aspect, the invention,

Ethylene polymer (a);

Ethylenically unsaturated functionalized organic compounds (b) and

Branched block ethylene polymers, including reactive thermoplastic polymers (c) capable of reacting with ethylenically unsaturated functionalized organic compounds to form side chained block ethylene polymers.

In another preferred aspect, the present invention,

(i) the M _w / M _n ratio measured by gel permeation chromatography is less than about 3.0, (ii) the density is about 0.93 g / cm 3 or less, and (iii) the Short Chain Branching Distribution Index is Uniform ethylene polymer (a) greater than about 30%;

Ethylenically unsaturated functionalized organic compounds (b) and

Branched block ethylene polymers, including reactive thermoplastic polymers (c) capable of reacting with ethylenically unsaturated functionalized organic compounds to form side chained block ethylene polymers.

In another aspect, the present invention,

(1) forming an ethylenically unsaturated functionalized organic compound into the side chain of the ethylene polymer to form a branched ethylene polymer,

(2) reacting an ethylene polymer, an ethylenically unsaturated functionalized organic compound and an ethylenically unsaturated organic compound, comprising reacting the reactive thermoplastic polymer with a branched ethylene polymer to form a branched block ethylene polymer Methods of making branched block ethylene polymers comprising reactive thermoplastic polymers.

In a preferred aspect, the present invention,

(1) forming an ethylenically unsaturated functionalized organic compound into side chains of a uniform ethylene polymer to form a branched uniform ethylene polymer,

(2) reacting the reactive thermoplastic polymer with the branched uniform ethylene polymer to form a branched block ethylene polymer, preferably (i) a M _w / M _n ratio as determined by gel permeation chromatography A homogeneous ethylene polymer (a), an ethylenically unsaturated functionalized organic compound (b) that is less than 3.0, (ii) has a density of about 0.93 g / cm 3 or less, and (iii) has a short chain branched distribution index greater than about 30% And a method for producing a branched block ethylene polymer comprising a reactive thermoplastic polymer (c) capable of reacting with an ethylenically unsaturated functionalized organic compound.

In another aspect, the invention provides a branched block ethylene polymer and thermoplastic comprising a ethylene polymer (a), an ethylenically unsaturated organic compound (b) and a reactive thermoplastic polymer (c) capable of reacting with the ethylenically unsaturated organic compound. Compositions comprising mixtures of mixed or shaped polymers.

In another preferred aspect, the present invention,

(i) homogeneous, _wherein the M _w / M _n ratio measured by gel permeation chromatography is less than about 3.0, (ii) the density is about 0.93 g / cm 3 or less, and (iii) the short-chain branched distribution index is greater than about 30%. Ethylene polymer (a);

Ethylenically unsaturated organic compounds (b) and

A composition comprising a mixture of a branched block ethylene polymer comprising a reactive thermoplastic polymer (c) capable of reacting with an ethylenically unsaturated organic compound and a thermoplastic blend or molding polymer.

In another aspect, the present invention,

(1) (a) an ethylenically unsaturated functionalized organic compound is added to the ethylene polymer to form a branched ethylene polymer, and then (b) reacting the reactive thermoplastic polymer with the branched ethylene polymer to form a branched block ethylene polymer. Forming branched block ethylene polymers,

(2) a process for preparing a composition from a thermoplastic mixed or molded polymer, an ethylene polymer, an ethylenically unsaturated functionalized organic compound and a reactive thermoplastic polymer, comprising mixing the branched block ethylene polymer with a thermoplastic mixed or molded polymer Include.

In a preferred aspect, the present invention,

(1) (a) an ethylenically unsaturated functionalized organic compound is added to a homogeneous ethylene polymer to form a branched homogeneous polymer, and then (b) a reactive thermoplastic polymer is reacted with a branched homogeneous ethylene polymer to side chain The side chain block ethylene polymer is formed by forming the type block ethylene polymer, and then

(2) a thermoplastic mixed or molded polymer comprising mixing the branched block ethylene polymer with a thermoplastic mixed or molded polymer; Homogeneous ethylene polymers having a M _w / M _n ratio measured by gel permeation chromatography of less than about 3.0, a density of about 0.93 g / cm 3 or less, and a short chain branched distribution index of greater than about 30%; Methods of making compositions from ethylenically unsaturated functionalized organic compounds and reactive thermoplastic polymers.

In one preferred aspect, the reactive thermoplastic polymer of component (c) is an amine functionalized polymer. In another preferred aspect, the reactive thermoplastic polymer of component (c) is a polyester.

Surprisingly, articles molded from the compositions of the present invention are polymers (a) grafted with a mixture of the corresponding polymers described in (a) and (c) (hereafter (a) / (c)) or only (b) In the following, useful temperature storage modulus beyond that indicated by (a) / (b)] is shown. That is, the branched block ethylene polymers of the present invention are softened and deformed at high temperatures, ie they exhibit a higher service temperature than the (a) / (c) mixture or (a) / (b) graft. In addition, the branched block ethylene polymers of the present invention surprisingly exhibit a lower tan delta than the (a) / (c) mixture or (a) / (b) graft.

1 to 18 are graphs (charts). Figure 1 shows the storage modulus (indicated by ***) of the branched block ethylene polymers of the present invention as compared to the control, which is not an example of the present invention. 2A and 2B show DMS rheology comparisons of the branched block ethylene polymers of the invention, denoted by Δ, as compared to the control, which is not an example of the invention. Figure 3 shows the tangent deltas of the branched block ethylene polymers of the present invention, E 'and E ". RMS rheological data at 190 ° C. Figure 5 shows the tan delta at 190 ° C. of the branched block ethylene polymers of the invention, denoted by ◇, as compared to the control, not an example of the invention. The RMS rheological data at 190 ° C. of the branched block ethylene polymers of the invention differing in ratio of homogeneous ethylene polymers grafted with maleic anhydride to reactive thermoplastic polymers represented by nylon. Side chains of the invention differ in the ratio of homogeneous ethylene polymers grafted with maleic anhydride to reactive thermoplastic polymers RMS rheological data of the rock ethylene polymer is shown at 230 ° C. Figure 8 shows the branched block ethylene polymers of the invention having different ratios of uniform ethylene polymer grafted with maleic anhydride to reactive thermoplastic polymers represented by nylon. The tan delta at 190 ° C. Figure 9 is 230 ° C. of the branched block ethylene polymers of the invention having different ratios of uniform ethylene polymer grafted with maleic anhydride to reactive thermoplastic polymers represented by nylon. It represents the tan delta at.

FIG. 10 shows a uniform ethylene polymer grafted with maleic anhydride (denoted MAHg8200, where 8200 is a representation of Engage ^™ 8200, an ethylene polymer) (not an example of the invention), and the graphed polymer is PCTG (polycyclohexanoldi RMS data at 190 ° C. is compared for side chain block ethylene polymers formed by reacting with methol terephthalate glycol), PET (polyethylene terephthalate) and nylon 6. FIG. 11 shows RMS data at 190 ° C. for MAHg8200 (as described above) and branched block ethylene polymers formed by reacting the graphed polymer with nylon 6, nylon 11 and nylon 12. FIG. 12 is the same comparison as FIG. 11, but performed at 230 ° C. FIG. FIG. 13 shows how the rheology index is improved by adding various% nylon 6 to MAHg8200. FIG. 14 shows how melt strength is improved by adding various percentages of nylon 6 to MAHg8200. FIG. 15 shows the viscosity of a branched block ethylene polymer comprising nylon 6 grafted with a homogeneous ethylene polymer represented by XU58300 (ethylene polymer sold by The Dow Chemical Company) through maleic anhydride. It shows the effect of oil on. FIG. 16 shows the effect of oil on tangent delta of branched block ethylene polymer comprising nylon 6 grafted into homogeneous ethylene polymer represented by XU58300 (ethylene polymer sold by The Dow Chemical Company) through maleic anhydride. Figure 17 shows various branched block ethylenes including various reactive thermoplastic polymers, namely nylon 6 grafted with MAHg8200 through PPO / HIPS (polyphenylene oxide / high impact polystyrene), PCTG, PET and maleic anhydride Comparison of polymers Figure 18 shows Shore A hardness at various temperatures, as achieved by branched block ethylene polymers comprising 70 weight percent MAHg8200 and 30 weight percent nylon 6.

FIG. 19 is a rotational speed measured by rheometric (dynamic) mechanical spectroscopy at 230 ° C. for a composition containing 75% polypropylene and 0, 10, 15, 20, 25 and 30% branched block ethylene polymers. The viscosity associated with is shown.

FIG. 20 shows the rotational speed measured by rheometric (dynamic) mechanical spectroscopy at 230 ° C. for a composition containing 75% polypropylene and 0, 10, 15, 20, 25 and 30% branched block ethylene polymers. It shows the tan delta associated with.

In the figure, ITP is a substantially linear ethylene polymer, PBT is polybutylene terephthalate, MAH is maleic anhydride, and MMA / GMS is described again in the Examples of the present invention, as shown in the example of 98: 8: 2. Methacrylate-butylacrylate-glycidyl methacrylate. DMS is Dynamic mechanical spectrometry and RMS is Rheolometric mechanical spectrometry. Akronim POE is also used for polyolefin elastomers in the figure for homogeneous ethylene polymers. RSA is a Rheometric Solids Analyzer.

The compositions of the present invention are useful for applications in which impact modified polymers are used. These include, for example, films, fibers, coatings, extruded sheets, multilayer laminates and shaped articles of virtually all kinds, in particular profiled extrusion gaskets, blow molded or thermoformed products, automotive dashboards, body shaping and interior parts, and automobiles, It is useful in the manufacture of other parts and members useful for the electrical and electronics industries. The compositions of the present invention are also useful as hot melt adhesives. The process of the invention is useful in the preparation of polymers, compositions and shaped articles having the same or similar uses as described above.

The branched block ethylene polymers of the present invention are surprisingly useful as rheology modifiers, impact strength modifiers and melt strength enhancers. The effect of the modifier is a function of the melt elasticity, dispersibility and miscibility of the branched block ethylene polymer. Branched block ethylene polymers are useful for blow molding and thermoforming. They are also usefully used for oil stretching. In addition, especially where the reactive thermoplastic polymer is an amine functionalized polymer (eg nylon), branched block ethylene polymers are useful for forming non-crosslinked foams that can be recycled. In the case of branched block ethylene polymers in which the reactive thermoplastic polymer is nylon, the branched block ethylene polymers using nylon 11 as the reactive thermoplastic polymer provide the best melt strength, followed by the use of nylon 6, and then Is when nylon 12 is used.

Detailed description of the invention

The branched block ethylene polymers of the present invention are ethylene polymers, preferably polymers having an M _w / M _n ratio of less than about 3.0, as defined by gel permeation chromatography, more preferably uniform ethylene polymer (i); It is made from ethylenically unsaturated functionalized organic compounds (ii) and reactive thermoplastic polymers (iii) capable of reacting with ethylenically unsaturated functionalized organic compounds. The ethylene polymer can be considered as the first polymer block. The ethylenically unsaturated functionalized organic compound is added to the ethylene polymer through its double bond to form a branched ethylene polymer. If the side chain formed by the ethylenically unsaturated functionalized organic compound has a sufficient length (eg contains three or more molecules), the second block itself can be formed. However, the side chains can only be formed by single molecules of ethylenically unsaturated functionalized organic compounds. Regardless of the length of the side chains formed by the ethylenically unsaturated functionalized organic compounds, the side chain ethylene polymers are functional with respect to the residues of the ethylenically unsaturated functionalized organic compounds, reacting with the reactive thermoplastic polymer to form the final polymer block. Form.

The side chain points containing the residues of one or more molecules of the ethylenically unsaturated functionalized organic compound and allowing the bonding of the reactive thermoplastic polymer as the final polymer block are ethylene and (optional) other monomer (s) (e.g. alpha-olefins) ) Can be distinguished from long chain side chains and short chain side chains which may be caused to the ethylene polymer during its formation. The side chain points formed from ethylenically unsaturated functionalized organic compounds are added to the ethylene polymer after its original polymerization reaction, in contrast to the side chains formed in connection with the skeletal growth during the polymerization of ethylene, thus the final polymer of the branched block ethylene polymer As a block it provides the necessary reactive sites for the bonding of the reactive thermoplastic polymer.

Subsidiary Component (a)-Regarding Ethylene Polymers

Subcomponent (a) is an ethylene polymer which forms the first block in the preparation of the branched block ethylene polymer of the invention. Ethylene polymers useful for this purpose may include, in particular, conventional ethylene polymers such as low density polyethylene (“LDPE”), linear low density polyethylene (“LLDPE”), and high density polyethylene (“HDPE”). LDPE is usually prepared under high pressure conditions and is known to have a density of about 0.915 to about 0.935 g / cm 3. This low density results from the region of many amorphous arrays which are characteristic of LDPE due to their long chain side chains, most of which are longer than the backbone. Compared to purely crystalline polyethylene having a density of 0.97 g / cm 3, since the density of purely amorphous polyethylene is 0.855 g / cm 3, it can be seen that LDPE has some crystallinity. However, its long chain branching is its main property. LDPE usually has as many as 4 to 25 and often as many as 90 long chain side chains per 1000 carbon atoms. It also has 10 to 35 short chains, each containing 2 to 8 carbon atoms per 1000 carbon atoms, which backbiting along the backbone during chain growth, rather than from incorporation of comonomers as in the case of LLDPE. And molecular rearrangements.

LDPE can be prepared in a tubular reactor or in a stirred autoclave, where a heated and pressurized feed stream of ethylene gas, free radical initiators and any chain transfer agents is injected into the reaction apparatus. The formation reaction usually takes place at a temperature not exceeding 1,500 to 3,000 atm (152 sowl 304 MPa) and usually 300 ° C., as is known in the art. During the polymerization of LDPE, ethylene can be copolymerized with other monomers such as vinyl acetate, ethyl acrylate, acrylic acid, vinyl chloride or carbon monoxide.

LLDPE is formed under low pressure conditions, which are usually considered to be suitable for forming HDPE. However, low density (0.910 to 0.940 g / cm 3) product is produced because ethylene is copolymerized with one or more α-olefins, rather than forming a homopolymer, which in the final product has the form and function of short side chains. Since the most commonly used comonomers are α-olefins such as 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene, these side chains prevent the filling of the dense and fully crystalline forms of representative HDPE. However, they are not as long as the fully branched long side chains associated with LDPE produced under high pressure conditions. LLDPE can be formed as a slurry in a light hydrocarbon diluent using a supported chromium catalyst or as a slurry in hexane using an organometal-titanium type catalyst. It may also be formed as a suitable hydrocarbon in solution at 250 ° C. or in the gas phase, as described in Levine US Pat. No. 4,011,382 or Jezl US Pat. No. 4,129,729.

HDPE homopolymers or copolymers typically have a crystallinity of about 94% and a density of greater than about 0.935 g / cm 3, in particular from about 0.950 to about 0.970 g / cm 3. HDPE has a higher melting point than LDPE due to its much higher crystallinity and density-115 ° C to 135 ° C. Crystalline HDPE homopolymers have regular linearity and, when cooled, form regular aggregates, referred to as crystals, from which HDPE obtains an excellent degree of stiffness and shatter-resistant character. . If ethylene is copolymerized with α-olefins as described above, or if short chain branching results from side reactions inherent to a particular reaction mechanism, crystallization is hindered in HDPE and the density is correspondingly reduced. For example, HDPE prepared using Ziegler transition metal catalysts may have about 0.5 to 4 short side chains, especially methyl groups, per 1000 carbon atoms. The molecular weight of HDPE is usually in the range of 50,000 to 1,000,000 or more. Beyond a certain point, the molecular weight of the HDPE is actually increased to decrease the density due to the chain entanglement, but the effect is not significant. Most aspects of HDPE strength decrease with decreasing molecular weight. HDPE can be prepared in a slurry system where high purity ethylene is fed to a loop reactor containing low boiling hydrocarbons used to dissolve ethylene and suspend catalyst and polymer particles. Alternatively, HDPE can be prepared in a gas phase process where no hydrocarbon diluent is used and the fluidized bed is used to stir and suspend polymer particles. The preparation of HDPE is more particularly described in Hogan, US Pat. No. 2,825,721.

Regarding the Use of Uniform Ethylene Polymers as Subcomponent (a)

Preferably, subcomponent (a) will be a homogeneous ethylene polymer. Homogeneous polymers are characterized by having a polydispersity (M _w / M _n ) and a uniform short chain branched distribution. The polydispersity (M _w / M _n ) of the homogeneous ethylene polymer described herein can be determined from the data generated by gel permeation chromatography (GPC). A commonly used instrument for this is a Waters 150 ° C. high temperature chromatography unit equipped with three mixed pore bed columns (Polymer Laboratories 103, 104, 105 and 106) operating at a system temperature of 140 ° C. The solvent used is 1,2,4-trichlorobenzene, from which a 0.3% by weight solution of the sample is prepared for injection. The flow rate is 1.0 ml / min and the injection size is 200 μl.

Molecular weight determinations on polyethylene are performed using polystyrene standards (from Polymer Laboratories) of narrow molecular weight distribution in terms of their elution volumes. Equivalent polyethylene molecular weights are described in the appropriate marks for polyethylene and polystyrene, as described in Williams and Word in Journal of Polymer Science, Polymer Letters, volume 6, page 621, 1968. Using the Mark-Houwink coefficient,

M _polyethylene = a * (M _polystyrene ) ^b

(Where a is 0.4316, b is 1.0 and M is the molecular weight for polyethylene and polystyrene in 1,2,4-trichlorobenzene). The weight average molecular weight M _w is expressed by the formula M _w = Σ Calculate in a conventional manner according to w _i * M _i , where w _i and M _i are the weight fraction and molecular weight of the i-th fraction eluted from the GPC column, respectively. The number average molecular weight M _n is conventionally determined according to the formula M _n = (Σ n _i * M _i ) / Σ n _i where n _i and M _i are the molecular number and molecular weight of the i th fraction eluted from the GPC column, respectively. Calculate by the method. The symbol * denotes a multiplication step.

The polydispersity (M _w / M _n ) for the homogeneous ethylene polymers described herein is less than about 3.0, preferably about 1.5 to about 2.5, more preferably about 1.7 to about 2.3, most preferred It is about two.

If they are ethylene / α-olefin interpolymers, the homogeneous ethylene polymers have a homogeneous side chain distribution. The terms "homogeneously branched" and "homogeneous branching distribution" mean that (1) the α-olefin comonomer (s) is randomized within a given molecule of the ethylene / comonomer copolymer Distributedly; (2) substantially all copolymer molecules have the same ethylene / comonomer ratio; (3) the polymer is characterized by a narrow short chain branched distribution; (4) the polymer is essentially devoid of measurable high density crystalline polymer fractions (eg, as measured by techniques such as including fractional polymer elution as a function of temperature); (5) The polymer is 21 C.F.R. When measured from the conditions described in 177.1520 (c) and (d), (i) ethylene / 1 at a density greater than about 0.90 g / dl of extractability of substantially reduced levels of n-hexane Less than 1% extractable to the octene copolymer) or (ii) a substantially amorphous (eg, ethylene / 1-octene copolymer), which is present when polymers greater than 75% by weight are soluble under specified conditions 90% is soluble at a density of g / cm 3 and 100% is soluble at a density of about 0.88 g / cm 3).

Typically, homogeneous ethylene polymers have a uniform short chain branched distribution and do not have a measurable high density fraction, ie these polymers are prepared by the Temperature Rising Elution Fractionation described in US Pat. No. 5,089,321. In the case of the measurement, the degree of branching does not contain polymer fractions of up to 2 methyl / 1000 carbons.

The uniformity or intolerance of the branching distribution is again represented by a Composition Distribution Branch Index ("CDBI") or Short Chain Branch Distribution Index ("SCBDI") value. CDBI is defined as the weight percent of polymer molecules whose comonomer content is within 50% of the average total molar comonomer content. CDBIs of polymers are described in, for example, temperature rising elution fractionation, as described in Wild, Journal of Polymer Science, Polymer Physics Edition, Volume 20, page 441 (1982) or US Pat. No. 4,798,081. It is easily calculated by The CDBI for the homogeneous ethylene / α-olefin interpolymers used in the present invention is greater than about 30%, preferably greater than about 50%, more preferably greater than about 80%, most preferably about 90% Greater than

Homogeneous ethylene polymers, by definition, are heterogeneously branched, prepared using a Ziegler-Natta polymerization process (eg, as described in Anderson, US Pat. No. 4,076,698). Linear low density polyethylene or linear high density polyethylene, or branched high pressure free radical polyethylenes and other high pressure ethylene copolymers known to those skilled in the art as having many long chain side chains, such as ethylene / vinyl acetate or ethylene / vinyl alcohol copolymers ) Is not included.

The degree of uniform ethylene polymer in the ethylene / α-olefin interpolymer, when measured by differential scanning calorimetry (DSC) at 30 to 150 ° C., has only one melt peak. This is in contrast to Ziegler polymerized heterogeneously branched linear ethylene polymers having two or more melt peaks due to the wide branching distribution. However, for certain groups of homogeneous ethylene polymers having a density from about 0.875 g / cm 3 to about 0.91 g / cm 3, the single melt peak is less than 12%, typically less than 9%, of the total heat of fusion of the polymer, depending on the device sensitivity. The lower surface of the melting peak (ie, below the melting point), which typically occupies less than 6%, may indicate "shoulder" or "hump". This processing structure is due to the chain transformation in the polymer and is distinguished on the basis of the slope of the single melting point peak monotonously changing through the melting point region of the processing structure. This processing structure is produced at 34 ° C., typically 27 ° C. and more typically at 20 ° C. of the melting point of a single melt peak.

Single melt peaks are measured using differential scanning calorimetry normalized to indium and deionized water. The method “applies first heat” about 5 samples of 7 mg size to about 150 ° C., held for 4 minutes, then cooled to 30 ° C. at 10 ° C./min, held for 3 minutes, and “ Secondary heating " heating to 150 ° C. at 10 ° C./min for heat flow. The total heat of fusion of the polymer is calculated from the area under the curve. If present, the heat of fusion due to the processing structure described above can be measured using an analytical balance and weight percent calculation.

One known group of homogeneous ethylene polymers is “uniform linear ethylene polymers”. Homogeneous ethylene polymers are not long chain branched, as defined below. The term “linear” refers to bulk high pressure side chained polyethylene, ethylene / vinyl acetate copolymers, or ethylene / vinyl alcohol copolymers, as long as it is known to those skilled in the art that these types of polymers have numerous long chain side chains. Does not mean.

Homogeneous linear ethylene polymers are selected from known polymer groups, examples of which are described in US Pat. No. 3,645,992 (Elston), prepared using so-called single site catalysts in batch reactors with relatively high ethylene concentrations [ As described in US Pat. No. 5,026,798 (Canich) or US Pat. No. 5,055,438 (Canich) and prepared using a geometric catalyst constrained in a batch reactor having a relatively high olefin concentration [US Pat. No. 5,064,802 ( Stevens) or as described in European Patent Application No. 416 815 (Stevens). These polymers are free of long chain branching, as described by Van der Sanden and Halle (Tappi Journal, February 1992). Processes using metallocene catalysts to produce homogeneous linear ethylene polymers are described, for example, in US Pat. Nos. 4,937,299, EP 129,368, EP to Ewen, each incorporated herein by reference. 260,999, US Pat. Nos. 4,701,432, 4,937,301, 4,935,397, 5,055,438 and WO 90/07526. Such polymers may be prepared by conventional polymerization processes such as gas phase polymerization, slurry polymerization or solution polymerization.

A preferred known group of homogeneous ethylene polymers is the "substantially linear ethylene polymer" and is characterized by a low degree of processability, eg susceptibility to melt fracture, even under conditions of high shear stress. Substantially linear ethylene polymers have a critical shear rate at the onset of surface melt crushing and substantially lower processing index than linear polyethylene at the same molecular weight distribution and melt index. Substantially linear ethylene polymers have the ease of shear thinning and processability similar to highly branched low density polyethylene (LDPE), as well as the strength and stiffness of linear low density polyethylene (LLDPE). Substantially linear ethylene polymers described in the present invention and methods for their preparation are disclosed in U.S. Patents 5,272,236, 5,278,272 and U.S. Pat. It is also described in SN 08 / 301,948.

As used herein, "substantially linear ethylene polymer" means that in addition to the short chain side chains resulting from comonomer incorporation, the polymer is also characterized by having long chain side chains. A substantially linear ethylene polymer has a melt flow ratio I ₁₀ / I ₂ is 5.63 or more, a molecular weight distribution M _w / M _n (A, as measured by gel permeation chromatography), the I ₁₀ / I ₂ - is equal to or smaller than 4.63, the surface The critical shear rate at the onset of melt fracture is 50% higher than the linear ethylene polymer having a critical shear stress at the onset of surface melt fracture that is essentially greater than I ₂ and M _w / M _n and / or about 2.8 × 10 ⁶ dyne / cm 2. It is characterized by greater than.

According to Ramamurthy in Journal of Rheology, 30 (2), 337-357, 1986, surface melt fracture may occur above a certain critical flow rate, which results in more severe "shark skin" from loss of specularity. It can represent the irregularity of the range in the form of. As used herein, the onset of surface melt fracturing is characterized by initiating a loss of extrudate gloss in which the surface roughness of the extrudate can only be detected by 40 × magnification. Substantially linear ethylene polymers also feature a critical shear rate at the start of surface melt crushing of at least 50% greater than the critical shear rate at the start of surface melt crushing of the linear olefin polymer having approximately the same I ₂ and M _w / M _n . It is done. Plots of apparent shear stress versus apparent shear rate are described in Shida et al., Polymer Engineering Science, Volume 17, No. 11 (1977), page 770 and in Rheometers for Molten Plastics by John Dealy, Van Nostrand Reinhold. To identify melt fracture phenomena over a nitrogen pressure range of 5250 to 500 psig using a die or gas extrusion rheometer (GER) test apparatus as described in Co. (1982), pages 97-99). use. According to the Ramamurthy in Journal of Rheology, 30 (2), 337-357 (1986), the irregularities of the extrudate observed above certain critical flow rates are broadly two major forms, surface melt crushing and total melt crushing. Can be classified as

Surface melt crushing certainly occurs under steady-state conditions and is specifically in the range from the loss of specular gloss to a more severe "shark skin" form. In this technique, the onset of surface melt fracturing is characterized by the onset of loss of extrudate gloss, where the surface roughness of the extrudate can only be detected by 40 × magnification. The critical shear rate at the onset of surface melt crushing for substantially linear ethylene polymers is conventional, with respect to I ₂ , polydispersity and density being 90 to 110% of the corresponding values for substantially linear linear ethylene polymers, respectively. At least 50% greater than the critical shear rate at the onset of surface melt crushing for the linear ethylene polymer. Preferably, the critical shear stress at the onset of surface melt fracture for the substantially linear ethylene polymer is greater than about 2.8 × 10 ⁶ dyne / cm 2.

Total melt crushing occurs under abnormal flow conditions, and in particular ranges from regular surface deformation (eg, roughness and smoothness or deformation of spiral patterns) to random deformation. For normal tolerability (eg in blown film products), surface defects should be minimal if not present. In the present invention, the critical shear rate at the onset of surface melt fracture (OSMF) and the critical shear stress at the onset of gross melt fracture (OGMF) are the surface roughness of the extrudate produced by GER. And change in form. For the substantially linear ethylene polymers described herein, the critical shear stress at the onset of total melt fracture is preferably greater than about 4 × 10 ⁶ dyne / cm 2.

In the GER melt fracturing measurement and the work index (PI) measurement described below, the substantially linear ethylene polymer is tested in the presence of an aluminum catalyst residue of 20 ppm or less in the absence of an inorganic filler. In these measurements, the polymer preferably contains an antioxidant such as phenol, hindered phenol, phosphite or phosphonite, preferably a mixture of phenol or hindered phenol and phosphite or phosphonite.

Another indicator of improved processability of substantially linear ethylene polymers is the rheological processability index (PI). PI is the apparent viscosity of the polymer and is measured by a gas extrusion rheometer (GER). GER is described above in connection with the measurement of melt fracture phenomena. The work index is measured at 190 ° C. under a nitrogen pressure of 2500 psig. In the case of highly flowable polymers (e.g. polymers with I ₂ of 50 to 100 g / 10 min. Or more), the diameter is 0.0296 inch (752 μm), preferably 0.0413 inch, and the length / diameter ratio is 20: 1 A die with 180 ° bow angle is used.

Machining index is the following formula

Where 2.15 x 10 ⁶ dyne / cm 2 is the shear stress at 2500 psi and the shear rate is

Is the shear rate at the wall as indicated by {'where Q' is the extrusion rate in g / min, 0.745 is the melt density of the polyethylene in g / cm < 3 > Calculated in millipoise from.

PI is the apparent viscosity of the material measured at an apparent shear stress of 2.15 x 10 ⁶ dyne / cm 2.

For substantially linear ethylene polymers, PI is that of conventional linear ethylene polymers, with respect to that I ₂ , M _w / M _n and the density are 90 to 110% of the corresponding values for the substantially linear linear ethylene polymers, respectively. 70% or less.

Substantially linear ethylene polymers also have improved melt elasticity or melt tension as compared to uniform linear ethylene polymers. The "melt tension" is measured by a specially designed pulley transducer connected to the melt indexer. Melt tension is the load exhibited by the filament extrudate while passing the pulley over a 2 inch drum rotating at a standard speed of 30 rpm. Melt tension measurements are similar to those performed by a "melt tension tester" manufactured by Toyoseiki, and described by John Dealy (Rheometers for Molten Plastics, Van Nostrand Reinhold Co. (1982)). , pages 250-251. The melt tension of the substantially linear ethylene polymers described herein is at least about 2 g, in particular for polymers of narrow molecular weight distribution (e.g., about 1.5 to 2.5), the melt tension is usually at least about 5%, With respect to the index, polydispersity and density being 90 to 110% of the corresponding value for the substantially linear linear ethylene polymer, respectively, it may be about 60% greater than the melt tension of conventional linear ethylene interpolymers.

Another unique property of these substantially linear ethylene polymers is the flow properties _{where the} I ₁₀ / I ₂ values are essentially independent of the polydispersity (M _w / M _n ). This conventional Ziegler polymerized heterogeneous polyethylene resins and conventional single-site-significantly different uniform polyethylene resin catalyzed polymerization and, and, when its rheological properties is the polydispersity (M _w / M _n) increases, I ₁₀ / Allow the I ₂ value to also increase. Note that it is not necessary to add a peroxide to the substantially linear ethylene polymer in order for the polymer to exhibit I ₁₀ / I ₂ values independent of polydispersity (M _w / M _n ) and melt fracture properties.

In general, the I ₁₀ / I ₂ ratio of the substantially linear ethylene polymer is at least about 5.63, preferably at least about 7, in particular at least about 8, and most preferably at least about 9. The only limitation to the maximum I ₁₀ / I ₂ ratio is practical considerations such as economic or polymerization processes, but usually the maximum I ₁₀ / I ₂ ratio does not exceed about 20, preferably does not exceed about 15. In contrast, the I ₁₀ / I ₂ ratio of the uniform linear ethylene polymers described herein is generally 6 or less.

It is believed that the useful melt elasticity and processability of substantially linear ethylene polymers will result from their preparation. The polymers may be prepared by continuous (as opposed to batch) controlled polymerization using one or more reactors as described, for example, in WO 93/07187, WO 93/07188 or WO 93/07189. It can be prepared through. However, these polymers can also be prepared at temperatures and pressures sufficient to produce interpolymers with the desired properties using multiple reactors using, for example, multiple reactor forms as described in US Pat. No. 3,914,342. have.

Polymerization conditions for producing substantially linear ethylene polymers are generally useful conditions for solution polymerization, although slurry and gas phase polymerization are also useful, provided that appropriate catalyst and polymerization conditions are used. Multiple reactor polymerization processes, such as those described in US Pat. No. 3,914,342, are also useful for this purpose. Multiple reactors can be operated continuously or in parallel, wherein one or more confined geometry catalysts are used in one or more reactors.

In general, the continuous polymerization process is a condition known in the art for polymerization reactions in the Ziegler-Natta or Kaminsky-Sinn form, for example, temperatures from about 0 to 250 ° C. and atmospheric pressures to 1000 It is usefully performed at a pressure of 100 MPa. The support can be used, but preferably the catalyst is used in a homogeneous way (ie soluble). Of course, active catalyst systems are formed in situ when the catalyst and its cocatalyst components are added directly to the polymerization process, and it can be seen that suitable solvents or diluents, including condensed monomers, are used. However, prior to addition to the polymerization mixture, it is preferred to form the active catalyst in a separate step in a suitable solvent.

Preferably, the term “substantially linear ethylene polymer” indicates that the bulk polymer is substituted with an average of about 0.01 to about 3 long chain side chains / 1000 total carbon atoms (including both main and side chain carbons). Preferred polymers have from about 0.01 to about 1 long chain side chain / 1000 total carbon atoms, more preferably from about 0.05 to about 1 long chain side chain / 1000 total carbon atoms and in particular from about 0.3 to about 1 long chain side chain / 1000 Substituted by total carbon atoms.

As used herein, the term "backbone" refers to a separate molecule, and a solvent "polymer" or "bulk polymer" means a polymer as formed in a reactor in the conventional sense. The term “bulk” polymers means polymers that are produced from the polymerization process and, in the case of these substantially linear ethylene polymers, include both molecules that are long-chain branched, as well as molecules that do not cause long-chain branching. Thus, "bulk" polymers include all molecules formed during polymerization. In the case of substantially linear ethylene polymers, not all molecules are long chain branched, so that the average long chain branched content of the bulk polymer can beneficially affect the melt rheology (ie, melt fracture properties) of the bulk polymer. It can be seen that a sufficient number of molecules are long chain branched. If the polymer is an "substantially linear" ethylene polymer, the polymer should have at least enough long chain branched molecules such that the average long chain branching of the bulk polymer will be on average about 0.01 or more / 1000 total carbons.

When the long chain branched, substantially linear ethylene polymer is an ethylene / α-olefin interpolymer, the chain length of the long chain side chain may have one (1) or less carbons less than the number of carbons in the comonomer. In contrast, short chain side chains are defined as having a chain length of the same carbon number as the comonomer residues after incorporation into the polymer molecular backbone. For example, a substantially linear ethylene polymer that is ethylene / 1-octene has a backbone with long chain side chains that are at least 7 carbons in length, but also have short chain side chains that are only six in length.

In ethylene / α-olefin interpolymers, the long chain side chains are longer than the short chain side chains resulting from incorporation of the alpha-olefin (s) into the polymer backbone. The conventional effect of the presence of long chain branching in the substantially linear ethylene / a-olefin interpolymer used in the present invention is the improvement quantified and expressed in the present invention as a result of gas extrusion rheometer (GER), as described above. Rheological properties and / or melt flow, I ₁₀ / I ₂ increase.

Long chain branching can be distinguished from short chain branching using ¹³ C nuclear magnetic resonance spectroscopy (NMR), and in the case of ethylene homopolymers and copolymers of ethylene and C ₂ -C ₆ α-olefins, see Journal Randall's method of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics, Volume C29, pages 285-297 (1989). In practice, however, the long chain side chain portion beyond the sixth carbon atom cannot be distinguished using conventional ¹³ C NMR to determine the exact length of the long chain side chain, and this analytical technique uses side chains having 7 carbon atoms and side chains having 70 carbon atoms. Indistinguishable

US Pat. No. 4,500,648, incorporated herein by reference, describes the long-chain branching frequency (LCBF) with the formula LCBF = b / M _w where b is the weight average number of long chain side chains per molecule, M _w Is the weight average molecular weight). Molecular weight averages and long chain branched properties are determined by gel permeation chromatography and intrinsic viscosity method.

Other known techniques are useful for determining the presence of long chain side chains in ethylene polymers, including ethylene / 1-octene inter polymers. These two methods are gel permeation chromatography (GPC-LALLS) combined with a low angle laser light scattering detector and gel permeation chromatography (GPC-DV) combined with a differential viscometer detector. The use of these techniques for long chain side chain discovery and theories presented are well described in the literature (see, eg, Zimm, GH and Stockmyer, WH, J. Chem. Phys., 17, 1301 (1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112).

On October 4, 1994, at the Federation of Analytical Chemistry and Spectroscopy Society (FACSS) in St. Louis, Missouri, they all belong to Dow Chemical Company. A. Willem deGroot and P. P. Steve Chum presented data indicating that GPC-DV is a useful technique for quantifying the presence of long chain side chains in substantially linear ethylene interpolymers. In particular, the level of long chain side chains in degrut and peak substantially linear linear ethylene homopolymer samples correlated well with the level of long chain side chains measured using ¹³ C NMR (Zimm-Stockmayer equation). It is measured using.

It was also found that the presence of degroot and high octene did not change the hydraulic capacity of the polyethylene sample in solution, and the molecular weight increase attributable to the octene short chain side chain could also be seen by subtracting the mole% of octene in the sample. By deconvoluting the contribution to the increase in molecular weight due to the 1-octene short chain side chains, the degroot and additives can be used to quantify the level of long chain side chains in the ethylene / octene copolymer where GPC-DV is substantially linear. Said that.

Digrots and peaks also show the long-chain side chaining side of the substantially linear ethylene polymer from the plot of Log (I ₂ , melt index) as a function of Log (GPC weight average molecular weight) measured by GPC-DV. Long branching is not comparable to that of high pressure, highly branched low density polyethylene (LDPE), using Ziegler type catalysts such as titanium complexes and conventional homogeneous catalysts such as hafnium and vanadium complexes. It can be seen that it is clearly distinguished from the prepared ethylene polymer.

In contrast to the term “substantially linear ethylene polymer,” the term “linear” lacks long chain side chains that the polymer can measure or represent, ie the polymer is substituted with an average of less than 0.01 long chains / 1000 carbons. In the present invention, long chain branching is defined as having a chain length of 6 carbons or more, and lengths exceeding this cannot be distinguished using ¹³ C NMR spectroscopy.

"Substantially linear ethylene polymers" are prepared using a constrained geometry catalyst and are characterized by a narrow polydispersity (molecular weight distribution) and a narrow comonomer distribution. As used herein, an "interpolymer" is a polymer of two or more comonomers, such as copolymers, terpolymers, or the like, in other words, by polymerizing ethylene and one or more other comonomers It means the polymer produced. Other basic properties of these substantially linear ethylene polymers include low residue contents (ie, low concentrations in substantially linear linear ethylene polymers, catalysts used to prepare polymers, unreacted comonomers, and low molecular weights prepared during polymerization). Oligomers) and controlled molecular structures that provide good processability despite the narrow molecular weight distribution compared to conventional olefin polymers.

While it is preferred to use substantially linear ethylene polymers in the preparation of branched block ethylene polymers, mixtures of two or more different kinds of ethylene polymers described above may also be used. Differences in the various types of ethylene polymers include, for example, (i) using conventional LLDPE with substantially linear ethylene polymers, or (ii) substantially linear with ethylene / a-olefin interpolymers that are substantially linear. Phosphorus ethylene homopolymers, (iii) two or more substantially linear ethylene polymers made using differently bound geometry catalysts, or (iv) two or more substantially made in different reactors or reaction zones. As a linear ethylene polymer or (v) two or more substantially linear ethylene polymers having different properties such as density, M _w / M _n , I ₂ or I ₁₀ / I ₂ . Differences between ethylene polymers included in this combination can demonstrate themselves, for example, in the form of multi-modal density, broad M _w / M _n and / or multiple melting point peaks. When used in combination, ethylene polymers can be usefully prepared using the double reaction polymerization method described below.

General Characteristics of Ethylene Polymers:

The ethylene polymer may be an ethylene homopolymer or an interpolymer of ethylene with one or more C ₃ -C ₂₀ α-olefin comonomers and / or one or more C ₄ -C ₁₂ diolefins. The ethylene polymer may also be an interpolymer of ethylene mixed with other unsaturated monomers with one or more of the above C ₃ -C ₂₀ α-olefin comonomers and / or diolefins. Often, the ethylene polymer is an interpolymer of ethylene with only one C ₃ -C ₂₀ α-olefin, more preferably ethylene and propene, isobutylene, 1-butene, 1-hexene, 4-methyl-1 Interpolymers of -pentene or 1-octene, interpolymers of ethylene and 1-octene are particularly preferred. Other monomers preferred for inter polymerization include styrene, halo or alkyl substituted styrenes, vinylbenzocyclobutene, 1,4-hexadiene and naphthenics such as cyclopentene, cyclohexene and cyclooctene.

Preferred ethylene polymers comprise 50 to 95% by weight of ethylene and 5 to 50% by weight, preferably 10 to 25% by weight of one or more comonomers. Comonomer content is measured using infrared spectroscopy according to ASTM D-2238, Method B.

The density of ethylene polymers is measured according to ASTM D-792 and is generally at least about 0.85 g / cm 3, often at least about 0.865 g / cm 3 and sometimes at least about 0.89 g / cm 3. The density of ethylene polymers is generally at most 0.96 g / cm 3, often at most 0.93 g / cm 3 and sometimes at most 0.90 g / cm 3. Density measurements are often made of polymers only, ie using polymers containing aluminum from catalyst residues not exceeding 20 ppm, in the absence of inorganic fillers.

In certain cases, the ethylene polymers described herein are crystalline and / or semicrystalline polymers. These are usually solid at room temperature and can be pelleted at ambient conditions or at temperatures induced by cooling water. For example, a substantially linear ethylene / 1-octene copolymer with a density of 0.865 g / cm 3 has a crystallinity of about 10% at room temperature.

The molecular weight of the ethylene polymer is easily indicated using ASTM D-1238, a melt index measurement according to conditions 190 ° C./2.16 kg (previously known as “Condition (E)” and also known as I ₂ ). The melt index value is inversely proportional to the molecular weight of the polymer. Therefore, although the relationship is not linear, the larger the molecular weight, the lower the melt index. Melt index I ₂ for ethylene polymers is generally at least about 0.01 g / 10 min (“g / 10 min”), preferably at least about 0.1 g / 10 min, and more preferably about 0.5 g / 10 min. Above, most preferably about 1.0 g / 10 min or more. The melt index I ₂ for ethylene polymers is generally about 1000 g / 10 min or less, preferably about 500 g / 10 min or less, more preferably about 250 g / 10 min or less, most preferably about 100 g / 10 min or less.

Use of a dual reactor system to make ethylene polymers:

Multiple reactors, as described in US Pat. No. 3,914,342, US SN 08 / 010,958, filed Jan. 29, 1993, and US SN 08 / 208,068, filed March 8, 1994. Multi-reactor polymerization methods that can operate continuously or in parallel are often useful for preparing ethylene polymers. When the reactors are operated in parallel, each polymerization product is mixed together in one mixture, while still in solution. If the multiple reactors are operated continuously, the product of the first reactor or reaction zone is passed to the second reactor or reaction zone and additional monomers and catalyst are added thereto.

To the extent that little residual catalyst, which is rarely present, is passed from the first reactor or zone to the second reactor or zone, the product exiting the second reactor or zone is not complete, but as if the reactors were run in parallel, Predominantly a mixture of individual polymers prepared separately in each reactor or zone. However, the ethylene polymers described in the present invention are believed to include products in which monomers are polymerized with the same polymer chain in both the first and second reactors or zones.

After combining the product streams exiting the parallel reactors, or continuously withdrawing the product from the final reactor or zone, the solvent is removed as is known in the art to recover all the polymers together as one product.

The various reactors or zones operated continuously or in parallel may differ in terms of properties such as the type of catalyst used, the type of α-olefin comonomers supplied to each, or the temperature at which each is operated. For example, constrained geometry catalysts can be used in one reactor or zone and Ziegler catalysts can be used elsewhere. If the reactors are operated in parallel, the combined stream or effluent from which the final product is recovered need not contain the same amount of output from each reactor.

Regarding the ethylenically unsaturated functionalized organic compound which is the subcomponent (b):

The ethylenically unsaturated functionalized organic compound, which is a minor component (b) used in the preparation of the branched block ethylene polymers of the present invention, contains carbon-carbon double bonds, for example by polygrafting Forms the side chain of the narrow ethylene polymer. For example, these ethylenically unsaturated functionalized organic compounds containing functional groups such as carbonyl groups (-C═O) (e.g. carboxylic acids or anhydrides) or epoxy rings, amines or alcohols can be functionalized or ethylenically unsaturated. The functionalized organic compound may be oxazoline.

Ethylenically unsaturated functionalized organic compounds containing at least one carbonyl group

Representative examples of such compounds containing one or more carbonyl groups are unsaturated carboxylic acids and their esters, anhydrides and salts thereof (both metallic and nonmetallic). Preferably, the organic compound contains ethylenic unsaturations conjugated with carbonyl groups. Representative compounds include, when present with acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methyl crotonic acid and cinnamic acid, esters, anhydrides and salt derivatives thereof. Maleic anhydride is a preferred ethylenically unsaturated organic compound containing at least one carbonyl group.

Ethylenically unsaturated functionalized organic compounds containing at least one epoxy ring

Representative examples of ethylenically unsaturated functionalized organic compounds containing at least one epoxy ring include, for example, glycidyl esters of unsaturated carboxylic acids (eg glycidyl methacrylate); Glycidyl ethers of unsaturated alcohols (eg allyl-glycidyl-ether) and glycidyl ethers of alkenylphenols (eg isopropenylphenyl-glycidyl ether) and vinyl and allyl esters of epoxycarboxylic acids (eg : Vinyl ester of epoxidized oleic acid). Other ethylenically unsaturated organic compounds containing one or more epoxy rings are described in US Pat. No. 5,369,154 (Laughner), which is incorporated herein. Among these, glycidyl methacrylate is preferable.

Ethylenically unsaturated functionalized organic compounds containing at least one amine function

Representative amines include amine compounds having one or more ethylenically unsaturated groups, such as allyl amine, propenyl amine, butenyl amine, pentenyl amine, hexenyl amine; Amine ethers including isopropenylphenyl ethyl amine ethers and their homologues (branched, cyclic and unbranched), vinyl and allyl ethers of amine compounds, vinyl and allyl esters of amine substituted acids, and the like. In each case, amines and unsaturations are present at positions where they do not undesirably interfere with the grafting reaction. In addition, the amines are alkyl groups (preferably about 1 to about 20 carbon atoms), aryl groups (preferably about 6 to about 30 carbon atoms), halogens, which are unsubstituted or do not undesirably interfere with the grafting reaction. Optionally substituted by specific groups such as ether and thioether groups.

Ethylenically unsaturated organic compounds containing at least one alcohol function

Representative alcohols are compounds containing a hydroxy group and at least one ethylenically unsaturated group, for example allyl and vinyl ethers of alcohol compounds such as ethyl alcohol and homologues thereof (branched, cyclic and unbranched), Compounds such as propenyl alcohol, butenyl alcohol, pentenyl alcohol, hexenyl alcohol, heptenyl alcohol, octenyl alcohol, etc., as well as vinyl and allyl esters of alcohol substituted, preferably carboxylic acids. In each case, alcohols and unsaturations are present at positions where they do not undesirably interfere with the grafting reaction. In addition, alcohols are alkyl groups (preferably about 1 to about 20 carbon atoms), aryl groups (preferably about 6 to about 30 carbon atoms), halogens, which are unsubstituted or do not undesirably interfere with the grafting reaction. Optionally substituted by specific groups such as ether and thioether groups.

Oxazoline compounds for use as ethylenically unsaturated functionalized organic compounds

Representative oxazoline compounds for use in the present invention include Wherein each J is independently a hydrogen, a halogen, a C ₁ -C ₁₀ alkyl radical or a C ₆ -C ₁₄ aryl radical.

The ethylenically unsaturated functionalized organic compound is added to the ethylene polymer to form a branched ethylene polymer, and then the portion of the branched ethylene polymer derived from the vinyl compound is from about 0.01% to about 10% by weight of the ethylenically unsaturated organic compound, preferably Preferably from about 0.1 to about 5 weight percent and more preferably from about 0.2 to about 2 weight percent.

Unfunctionalized vinyl compounds (e.g., ethylenically unsaturated aromatic compounds, such as styrene) may be substituted for some of the ethylenically unsaturated functionalized organic compounds, provided that they do not form the branched block ethylene polymers of the present invention. Sufficient functionalized ethylenically unsaturated organic compounds exist as branching points for reacting with the reactive thermoplastic polymer of subcomponent (c).

Ethylenically unsaturated functionalized organic compounds can be grafted into ethylene polymers by techniques known to those skilled in the art, as taught in US Pat. Nos. 3,236,917 and 5,194,509. For example, in the '917 patent, the polymer is introduced into a two-roll mixer and mixed at a temperature of 60 ° C. The ethylenically unsaturated organic compound is then added together with the free radical initiator (eg benzoyl peroxide) and the components are mixed at 30 ° C. until the grafting reaction is complete. In the '509 patent, the method is similar except that the reaction temperature is higher (eg 210 to 300 ° C.) and no free radical initiator is used or at reduced concentration.

Another preferred grafting method, using a twin screw non-volatile extruder as the mixing device, is taught in US Pat. No. 4,950,541. The ethylene polymer and the ethylenically unsaturated organic compound are mixed and reacted in the extruder in the presence of the free radical initiator and the temperature at which the reactants melt. Preferably, the ethylenically unsaturated organic compound is introduced into the region maintained under pressure in the extruder.

Regarding the reactive thermoplastic polymer, which is subcomponent (c):

Reactive thermoplastic polymers, which are subcomponents (c) used in the preparation of the branched block ethylene polymers of the invention, are suitably prepared by condensation reactions of bifunctional monomers or by other methods known to those skilled in the art.

Reactive thermoplastic polymers are advantageously semicrystalline or amorphous polymers containing functional groups capable of reacting with functionalized ethylene polymers in melt mixing processes. Semicrystalline polymers preferably have a T _m greater than 70 ° C. Amorphous polymers have a T _g greater than 50 ° C. Suitable functional groups include hydroxy groups, phenolic groups, amines, epoxies and isocyanates. Examples of suitable reactive thermoplastic polymers include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), nylon-6, polysulfone, polyurethane, polycarbonate, epoxy functionalized polymethylmethacrylate, epoxy or other Functional groups, preferably styrene acrylonitrile functionalized as set forth above.

Typically, the reactive thermoplastic polymer is added to the branched ethylene polymer to form a branched ethylene block polymer, and then the portion of the branched ethylene block polymer derived from the reactive thermoplastic polymer is from about 1 to about 40 weight percent of the branched block ethylene compound. , Preferably from about 2 to about 30 weight percent and more preferably from about 5 to about 25 weight percent.

One suitable group of reactive thermoplastic polymers is the group known as engineering thermoplastics. Kirk-Othmer's third edition of the Scientific and Technical Dictionary of Engineering uses engineering resins as pure, unreinforced or filled thermoplastics that retain dimensional stability and most mechanical properties above 100 ° C and below 0 ° C. It is defined as The terms "engineering plastics" and "engineering thermoplastics" may be used interchangeably. Engineering thermoplastics include polyolefins, mixtures or alloys selected from acetal resins, polyamides (e.g. nylon), polyimides, polyetherimides, polyesters, liquid crystal polymers and the aforementioned resins, and other resin forms (e.g., polyethers). And some examples selected from high temperature polyolefins such as polycyclopentane, copolymers thereof, and polymethylpentane.

Regarding the Use of Amine Functionalized Polymers as Subcomponent (c)

One particularly suitable group of reactive thermoplastic polymers for use as subcomponent (c) is a group known as amine functionalized polymers. One of the amine functionalized polymers is polyamide, which can be prepared by the condensation reaction of difunctional monomers, usually monomers containing acid and amine functionality, wherein the monomers have the same or different functional groups. For example, when hexamethylenediamine is reacted with adipic acid, a polyamide of the form-[-AABB-]-is obtained, wherein the diamine and diacid units are interchanged. However, in the case where monomers such as amino acids or cyclic lactams are self polymerized, polyamides in the form of [-AB-]-are produced from conventional head-to-tail polymerization similar to the addition mechanism. do. For example, when producing nylon-6, it is heated to raise the temperature of caprolactam to 240 to 280 ° C. and a catalyst (eg water and phosphoric acid) is added to the system. The ring opening reaction occurs by hydrolysis, and as the polymerization reaction proceeds, unreacted monomers are removed from the system and recycled. The polycondensation reaction and the growth of the polymer chains are caused by the removal of water from the system.

Polyamides suitable for use in the present invention include the polymerization of two or more different diamines and / or different diacids and / or different amino acids together to form random or block co-polyamides. The polymer chains between functional groups can be linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbons. The chain may also contain hetero atoms (eg oxygen, sulfur or nitrogen). For example, block or random, such as melt mixing of two or more different polyamides, reactions of diamine or diacid monomers containing amide bonds with other diamines or diacids, or reactions of diisocyanates with dicarboxylic acids Copolymers are also suitable for use in the present invention.

Polyamides are most often prepared by direct amidation, in which the amine groups of diamines or amino acids are bonded to the carboxyl of diacids, with the removal of water. Derivatives of acid functional groups, such as esters, acyl halides or amides can be used as other sources of carboxyl functionality, in which case the by-products are alcohols, hydrogen halides or ammonia, respectively. Formation of polyamide can also occur by ring-opening polymerization of caprolactam, such as when nylon-6 is made from caprolactam. Suitable polyamides are nylon-11, nylon-12 and generally nylon with crystalline melting points below 280 ° C., often below 250 ° C. and sometimes below 230 ° C., or amorphous nylon.

The polyamides described above and methods of making them are described in more detail in US Pat. Nos. 2,071,253, 2,130,523 and 2,130,948.

Other examples of amine functionalized polymers include amine terminated butadiene / acrylonitrile rubbers or polymers having one or more primary aromatic groups, Lewis acid blocked primary aliphatic and / or secondary aliphatic or aromatic amine groups. do.

Suitable polyols, in particular polyethers and polyester polyols having secondary amine groups, are readily prepared by reacting the corresponding polyols with primary amines and reducing the resulting intermediates with hydrogen, as described in US Pat. No. 4,153,381. do. Secondary amines are usefully inertly substituted alkylamines, cycloalkyl amines or benzylamines. Alternatively, secondary aliphatic polyamine compounds can be prepared by the Michael addition reaction of the corresponding primary aliphatic amine with an ethylenically unsaturated compound. Acrylonitrile is a particularly suitable ethylenically unsaturated compound, although it is possible to use compounds which carry out the Michael addition reaction with primary amines. Primary aliphatic amines themselves can be prepared, for example, by reducing amination of the corresponding polyols and ammonia, as taught in US Pat. Nos. 3,128,311, 3,152,998, 3,654,370, 3,347,926 and 4,014,933. have.

Other suitable amine functionalized polymers are aromatic polyamines and include polyols, in particular polyethers and polyester polyols modified to contain aromatic amine groups. Such aromatic polyamines are, for example, by capping the corresponding polyether or polyester polyols with diisocyanates to form prepolymers, and then reacting the prepolymers with water to hydrolyze the free isocyanate groups to the corresponding primary amines. It can manufacture. In contrast, the compounds react the corresponding polyether or polyester polyols with p-nitro chlorobenzene, as taught in US Pat. No. 923,255 to Steuber et al., Filed October 27, 1986. It can then be prepared by reducing the nitro group with an amine. In another suitable process, the corresponding hydroxy or primary amine terminated polyethers or polyesters are reacted by transesterification with substances such as lower alkyl esters of p-aminobenzoic acids, in particular methyl esters, to produce aromatic polyamine compounds. can do. Secondary aromatic polyamines can be prepared by the Michael reaction of the corresponding primary aromatic amine compounds and ethylenically unsaturated compounds such as acrylonitrile, as described above.

Blocked primary aliphatic polyamines suitable for use in the present invention may be useful for reductive amination of ammonia with the corresponding hydroxy terminated compounds, followed by Lewis acids [e.g. benzoyl chloride, carbon dioxide and metal carboxylates (e.g. tin). , Zinc, titanium or aluminum carboxylate) and the like. Lewis acids are usefully employed in an amount of about 0.2 to about 5 equivalents, preferably about 0.9 to about 1.5 equivalents per primary amine group equivalent.

Various amine functionalized polymers suitable for use in the present invention can be represented by the following formula (I), (II), (III) or (IV).

[H (A) N] a--Ea-(E-G-E) b--N (A) H

[H (A) N] a-[E- (O-E) c] d-Od- [G- (O-G) c] e--N (A) H

[H (A) N] a--Q- [O-C (O) -Q-C (O) -O-Q] f--O-C (O) -Q-C (O) -O-Q--N (A) H

[H (A) N] a- (E-NH) j- (R2-G-R2-R3) h-R2-G-R2- (E-NH) j-N (A) H

In Chemical Formulas I, II, III, and IV,

A is each independently hydrogen or a C ₁ -C ₆ straight or branched chain alkyl or alkylene radical, which may be optionally interrupted by one or more nitrogen or oxygen atoms, wherein each carbon atom is attached to a primary or secondary amine group. Optionally substituted),

Each E is independently a straight, branched or interchain of C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ and more preferably C ₁ -C ₈ , which may be optionally blocked by one or more nitrogen or oxygen atoms Alkyl or alkylene radical that is clickable, wherein each carbon atom is a halogen atom (eg, a fluorine, chlorine, bromine or iodine atom), a C ₁ -C ₆ alkoxy group, a C ₆ -C ₁₀ aryloxy group, a phenyl group Optionally substituted by primary or secondary amine groups,

G is each independently, the following formula Wherein (I) Z is such that (A) all or different moieties are (i) straight, branched, cyclic or acyclic, (ii) aliphatic or aromatic, and / or (iii) saturated or unsaturated Divalent radicals composed of from 1 to 35 carbon atoms and up to 5 oxygen, nitrogen, sulfur, phosphorus and / or halogen (eg fluorine, chlorine and / or bromine) atoms, where each carbon atom is a primary or Optionally substituted with secondary amine groups), (B) S, S ₂ , SO, SO ₂ , O or CO, or (C) a single bond, and (II) X is each independently hydrogen, a halogen atom ( for example, fluorine, chlorine and / or bromine), alkyl click type between the C ₁ -C ₁₂ straight-chain or, alkoxy, aryl or aryloxy radicals (e.g., methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, Ethoxy, benzyl, tolyl, xylyl, phenoxy and / or xylyloxy) or primary or secondary amine groups, (III) g is 0 Or 1;

Q is independently at each occurrence E or G,

a is 0 or 1,

b is 0 to 10, preferably 0 to 4, more preferably 1 to 3, although both a and b cannot be 0,

c is 1 to 70, preferably 5 to 50, more preferably 5 to 30,

d and e are 0 or 1, although both d and e cannot be 0,

f is 0 to 70, preferably 5 to 50, more preferably 5 to 30,

R2 is independently at each occurrence a -E-CH (OH) -E- radical,

Is independently at each occurrence a -HN- (E-NH) j- radical,

h is 0 to 25, preferably 0 to 10, more preferably 1 to 3,

j is 1 to 6, preferably 1 to 4.

In the above equations, variables may have their respective values within subranges other than those specified or specifically stated.

The amine functionalized polymers generally have an average number of amine groups per molecule of at least about 0.75, preferably at least about 0.8, more preferably at least about 0.9 and most preferably at least about 1.0. The amine functionalized polymers generally have an average number of amine groups per molecule of about 3.5 or less, preferably about 3.0 or less, more preferably about 2.5 or less, and most preferably about 2.1 or less.

Amine functionalized polymers typically have an equivalent weight (defined as weight average molecular weight divided by the average number of amine groups) of about 400 to about 50,000, preferably about 600 to about 30,000, and more preferably about 800 to about 20,000. .

The amine functionalized polymer is not present in large amounts, which affects the desired benefits of the branched block ethylene polymer as a compositional modifier, but in an amount sufficient to form the final block of the branched block ethylene polymer of the present invention. Typically, the amine functionalized polymer is added to the branched ethylene polymer to form the branched ethylene block polymer, and then the branched ethylene block polymer portion derived from the amine functionalized polymer is from about 1 to about one side of the branched block ethylene polymer. It is used in an amount such that it can constitute about 40% by weight, preferably about 2 to about 30% by weight and more preferably about 5 to about 25% by weight.

For example, crystalline polar amine functionalized polymers (such as polyamides) are not generally believed to improve the performance of nonpolar ethylene polymers as modifiers in mixtures with thermoplastic molding polymers. However, when amine functionalized polymers (such as polyamides) are used in the amounts given above, they form not only the final blocks of the branched block ethylene polymers, but also the domains formed by the ethylene / vinyl compound copolymers. It was found to be morphologically dispersed. However, when amine functionalized polymers (such as polyamides) are used in amounts exceeding the amounts set forth above, they try to form their own crystalline domains in which the ethylene / vinyl compound copolymer is dispersed and such poly The brittleness of the amide domains complements the obtaining of the impact strength that the block terpolymers impart otherwise to the mixed composition. Likewise, if amine functionalized polymers with too high average amine functionality are used, crosslinking is likely to occur.

Regarding the use of polyester as reactive thermoplastic polymer of component (c):

Another group of reactive thermoplastic polymers useful as subcomponent (c) of the branched block ethylene polymers is polyesters. The polyesters can be prepared by self esterification of hydroxycarboxylic acids or by direct esterification, which is carried out by the self-growth reaction of diols and dicarboxylic acids with the removal of the resulting water-[-AABB-]-repeating units Providing a polyester having a. The reaction can be carried out in bulk or in solution with an azeotropic distillation of water using an inert high boiling solvent such as xylene or chlorobenzene.

Alternatively, in a similar manner, the ester forming derivatives of the dicarboxylic acids can be heated with the diols to obtain the polyesters in an ester interchange reaction. Suitable acid derivatives for this are alkyl esters, halides, salts or anhydrides of acids. The preparation of polyacrylates from bisphenols and aromatic diacids can be carried out essentially in the same interfacial system used in the preparation of polycarbonates.

Polyesters can also be prepared by ring-opening reactions of cyclic esters or C ₄ -C ₇ lactones, for which organic tertiary amine base phosphines and alkali and alkaline earth metals, hydrides and alkoxides can be used as initiators. have.

In addition to the hydroxycarboxylic acids, suitable reactants for the preparation of the polyesters used in the present invention are diols and dicarboxylic acids, one or both of which may be aliphatic or aromatic. Accordingly, polyesters which are poly (alkylene alkanedicarboxylate), poly (alkylene arylenedicarboxylate), poly (arylene alkanedicarboxylate) or poly (arylene arylenedicarboxylate) are described herein. Suitable for use The alkyl portion of the polymer chain can be substituted, for example, by halogen, C ₁ -C ₈ alkoxy group or C ₁ -C ₈ alkyl side chain, and the divalent hetero atom group (e.g. -O -, -Si-, -S- or -SO _2- ). The chain may also contain unsaturated and C ₆ -C ₁₀ nonaromatic rings. Aromatic rings may contain substituents such as halogen, C ₁ -C ₈ alkoxy or C ₁ -C ₈ alkyl groups and may be bonded directly to the polymer backbone and alcohol or acid functional groups or interference atoms at specific ring positions.

Common aliphatic diols used in the formation of esters are C ₂ -C ₁₀ primary and secondary glycols such as ethylene glycol, propylene glycol and butylene glycol. Alkaldicarboxylic acids often used are oxalic acid, adipic acid and sebacic acid. The diol containing a ring is, for example, 1,4-cyclohexylenyl glycol or 1,4-cyclohexane-dimethylene glycol, resorcinol, hydroquinone, 4,4'-thiodiphenol, bis- (4-hydroxyphenyl) sulfone, dihydroxynaphthalene, xylylene diol, or one of many bisphenols such as 2,2-bis- (4-hydroxyphenyl) propane. Aromatic diacids include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyletherdicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfondicarboxylic acid and dipenoxyethanedicarboxylic acid.

In addition to polyesters formed from only one diol and one diacid, as used herein, the term “polyester” includes random, patterned or block copolyesters, for example two or more different diols. And / or from two or more different diacids, and / or from other divalent hetero atom groups. Mixtures of such copolyesters, mixtures of polyesters derived from only one diol and diacid, and mixtures of polyesters prepared from both groups are all also suitable for use in the present invention, the term “polyester” All of them are included. For example, the use of cyclohexanedimethanol with ethylene glycol in esterification with terephthalic acid results in clear amorphous, particularly of the copolyester of interest. Mixtures of 4-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, terephthalic acid, 4-hydroxybenzoic acid and ethylene glycol or mixtures of terephthalic acid, 4-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl Liquid crystal polyesters derived from the mixture are also prepared.

Polyesters made from aromatic diacids, such as poly (alkylene arylenedicarboxylate) polyethylene terephthalates and polybutylene terephthalates, or mixtures thereof, which are aromatic polyesters, are particularly useful in the present invention. Polyesters suitable for use in the present invention also allow values outside this range, but may have an intrinsic viscosity of about 0.4 to 1.2.

Methods and materials useful in the preparation of the polyesters described above include Winfield, US Patent No. 2,465,319, Pengilly, US Patent No. 3,047,539, Schwarz, US Patent No. 3,374,402, Russell US Pat. No. 3,756,986 to East and US Pat. No. 4,393,191 to East.

In a preferred embodiment, the polyester is added to the ethylene / vinyl compound copolymer to form a branched block ethylene polymer, and then the branched block ethylene polymer portion derived from the polyester is from about 1 to about 30% by weight, preferably about 2 to about 20% by weight and more preferably about 5 to about 10% by weight. In another embodiment, for example, where a catalyst is used to accelerate the formation of the branched block ethylene polymer, the amount of polyester used is at least about 60% by weight of the branched block ethylene polymer, possibly about 70 A value outside this range may be acceptable, although it may constitute greater than or equal to about 80 weight percent or more. In another preferred embodiment, the polyester has a weight ratio between the amount of polyester contained in the branched block ethylene polymer and the amount of mixed or molded polymer contained in the composition, often greater than about 0.015 / 1 and less than about 0.30 / 1, sometimes It is used in an amount such that it is greater than about 0.02 / 1 and less than 0.10 / 1.

In another preferred embodiment, the polyesters used in the preparation of the branched block ethylene polymers have an intrinsic viscosity (IV) of less than about 0.85, usefully about 0.5 to about 0.8, preferably about 0.55 to about 0.75. Polyesters with a relatively low IV generally consist of shorter polymer chains than polyesters with a relatively high IV. Thus, a particular mass of low IV polyester contains more chain end groups than the same mass of high IV polyester. The formation of branched block ethylene polymers is dependent on the reaction of polyester end groups with side chain points formed from vinyl compounds of the ethylene polymer, in particular -OH end groups, for this purpose a polyester containing a relatively large number of end groups It is useful to use

Process for the preparation of the branched block ethylene polymer of the present invention:

The branched block ethylene polymers of the present invention are prepared by first forming side chains containing ethylenically unsaturated functionalized organic compounds in the ethylene polymer. This can be done using the techniques presented above, for example, the graft polymerization method taught in US Pat. Nos. 3,236,917, 5,194,509 and / or 4,950,541.

After forming ethylenically unsaturated functionalized organic compounds such as maleic anhydride into the side chains of the ethylene polymer, the preparation of the branched block ethylene polymers of the present invention can be completed by reactive extrusion of the branched ethylene polymer and the reactive thermoplastic polymer. Can be. The reactive end groups on the reactive thermoplastic polymer form chemical bonds and react in the molten state with the functionality of the functionalized organic compound side chain to add the final polymer block to the branched block ethylene polymer of the present invention. The reaction between the reactive thermoplastic polymer and the side chain formed from the ethylenically unsaturated functionalized organic compound can optionally be enhanced by a catalyst. Although this reaction optionally occurs in a Banbury mixer or other apparatus in which elevated temperature and high shear mixing can be applied to the reactants, typical profiles for carrying out this reaction in a 30 mm twin screw extruder are as follows: zone temperatures 150, 200, 250, 250, and 250 ° C .; 250 rpm; 70-85% torque and residence time of 30 seconds.

In the case of using an extruder for the production of branched block ethylene polymers, the separate components produced are usually fed in turn through separate inlets during one pass through one extruder for easier material handling. In the case of simultaneous reaction of an ethylene polymer, an ethylenically unsaturated organic compound and a reactive thermoplastic polymer, the presence of the reactive thermoplastic polymer may physically hinder the necessary access of the unsaturated organic compound in forming the side chain, so that the ethylenically unsaturated organic compound is an ethylene polymer. Side chains are formed in small amounts on top, or not at all.

Use of Catalysts in the Preparation of Block Ethylene Polymers of the Invention:

The reaction between the branched ethylene polymer and the reactive thermoplastic polymer for preparing the branched block ethylene polymer of the present invention is optionally improved by the presence of a catalyst. Such catalysts may include alkali metal or alkaline earth metal salts with a pKa of 7 or more and nitrogen containing organic bases. Catalysts that melt below the temperature at which the branched ethylene polymer and the reactive thermoplastic polymer react and at which temperature have low volatility are most effective.

Salts having a pKa of at least 7, useful as catalysts in the present invention, include cations whose representative examples are lithium, sodium, potassium, magnesium, calcium or barium and azide, acetate, benzoate, borate, Bromate, bromide, carbonate, carboxylate, chlorate, chloride, chlorite, chromate, cyanate, cyanide, dithionate, fluoride, formate, hydrogen carbonate, hydrogen phosphate, hydrogen sulphate, hydrogen sulfide, hydrogen sulfite, Hydroxide, hypophosphate, hypophosphite, iodate, iodide, iodide, molybdate, nitrate, nitrite, oxalate, oxide, perchlorate, permanganate, phosphate, phosphite, pyro Phosphate, selenate, silicate, sulfate, sulfimide, sulfite, sulfonate, Oh carbonate, a salt formed from a thiocyanate or a thiosulfate, etc., and the derivatives thereof anion.

Preferred salts for use as catalysts in the present invention can be derived from aromatic sulfimides as represented by the following formula wherein M ⁺ is an alkali metal ion (eg potassium ion).

Representative nitrogen-containing organic bases useful as catalysts in the present invention include acridine, analin, aziridine, benzidine, benzimidazole, isoquinoline, morpholine, picoline, piperazine, piperidine, purine, pyrazine, pyridine, Pyrimidine, pyrrolidine, quinazoline, quinoline, toluidine and valine and the like. In general, many aliphatic and aromatic amines and their derivatives, in substituted and unsubstituted form, can serve as catalysts in the present invention, most commonly tertiary amines such as triethylamine and pyridine.

The amount of catalyst used in the preparation of the branched block ethylene polymer of the present invention is about 100 to about 3,000 ppm by weight, preferably about 1,000 to about 2,000 ppm, based on the combined weight of the branched ethylene polymer and the reactive thermoplastic polymer. .

With respect to mixtures of addition blending or molding polymers and branched block ethylene polymers;

The branched block ethylene polymers of the present invention may be usefully dry mixed or melt mixed with one or more addition mixing or molding polymers. In one example, the branched block ethylene polymer may be dry mixed or melt mixed with the mixed or molded polymer and then molded or extruded into the molded article.

The branched block ethylene polymers of the present invention can be seen from the exemplary polymers shown in the figures that are effective rheology modifiers, effective melt strength enhancers, blow molding or thermoforming strength enhancers, effective oil expanding polymers and / or impact modifiers.

The formation of random physical mixtures from ethylene polymers, reactive thermoplastic polymers and thermoplastic mixing or molding polymers graft modified with ethylenically unsaturated functionalized monomers is distinct and distinct from mixtures of branched block ethylene polymers and mixed or molding polymers. . It can be distinguished by observing systems comprising ethylene polymers, ethylenically unsaturated functionalized monomers, amine functionalized polymers and mixed or shaped thermoplastic polymers.

In the case of random physical mixtures, ethylene polymers graft modified with ethylenically unsaturated functionalized polymers can be used as essentially elastomeric modifiers for one or more thermoplastic polymers, one of which is an amine functionalized polymer. When two or more thermoplastic polymers are present in the composition, ethylene polymers graft modified with ethylenically unsaturated functionalized polymers are usually used as elastomeric modifiers for each thermoplastic polymer to essentially the same extent. In contrast, where the branched block ethylene polymer is intended to be used as a modifier in a mixture with a thermoplastic blend or a molding polymer, if the branched block ethylene polymer is not successfully formed, the result is grafted with an ethylenically unsaturated functionalized polymer. The modified ethylene polymer is not different from the random physical mixture containing the amine functionalized polymer, such as one of the molding polymers, which acts as a modifier to the total content of the molding polymer.

Reactive thermoplastic polymers are first present to change the viscoelastic properties of ethylene polymers graft modified with ethylenically unsaturated functionalized monomers, and to convert essentially elastomeric modifiers into hard / soft fragment modifiers. The reactive thermoplastic polymer makes up the hard segment and the ethylene polymer makes up the soft segment. Accordingly, such hard segment / soft fragment modifiers, branched block ethylene polymers, act as modifiers for one or more mixed or shaped polymers. The reactive thermoplastic polymer in the branched block ethylene polymer as a whole part of the hard segment / soft fragment modifier performs a different action than that of other shaped polymers in a random physical mixture.

Suitable blended or shaped polymers include polymers in which the branched block ethylene polymers are miscible, and include both grafted and ungrafted olefin and non-olefin polymers. The branched block ethylene polymer may also be mixed with a substantially linear ethylene polymer, a common heterogeneous side chain or uniform side chain linear ethylene polymer, a non-olefin polymer that may or may not be grafted or a mixture of these polymers. have.

Examples of blended or molded polymers include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), polypropylene, ethylene-propylene copolymers, ethylene-styrene copolymers, polyiso Butylene, ethylene-propylene-diene monomer (EPDM), polystyrene, acrylonitrile-butadiene-styrene (ABB) copolymer, ethylene / acrylic acid (EAA), ethylene / vinyl acetate (EVA), ethylene / vinyl alcohol (EVOH) , Polymers of ethylene and carbon monoxide (including those described in US Pat. No. 4,916,208); Polymers of ethylene, propylene and carbon monoxide (EPCO) and polymers of ethylene, carbon monoxide and acrylic acid (ECOAA).

Examples of blended or shaped polymers are characterized by their miscibility with branched block ethylene polymers that prevent the melt blends from separating into separate polymer phases. When one or more of these mixed or shaped polymers are blended with one or more branched block ethylene polymers, they all exhibit sufficient miscibility with one another in one-to-one or in a mixture with at least one or more other polymers, thereby providing a polymeric component This does not separate into separate polymer phases, which can make extrusion processes difficult, such as extrudate surging, film band effects, and the like.

The amount of branched block ethylene polymer mixed with one or more other blended or molded thermoplastic polymers may vary depending on the nature of the mixed or molded thermoplastic polymer or polymers, the intended end use of the mixture, the presence or absence of additives and, where present, the properties thereof, etc. It can vary and depend on many factors, including.

Typically, the mixture comprises from 1 to about 50 parts, preferably from about 2 to about 40 parts and preferably from about 5 to about 30 parts of the branched block ethylene polymer. Likewise, the mixture usually comprises about 50 to about 99 parts, usefully about 60 to about 98 parts, and preferably about 70 to about 95 parts of a mixed or shaped thermoplastic polymer or polymers. The weight part number of the branched block ethylene polymer and the mixed or shaped polymer or polymers does not necessarily need to be a total of 100 parts by weight.

However, when the blending or molding polymer is the same in the composition of the reactive thermoplastic polymer forming the side chain of the branched block ethylene polymer, the total amount of the reactive thermoplastic polymer and the mixed or molded thermoplastic polymer is 30 parts per 100 parts by weight of the mixed composition, preferably Preferably 20 parts, more preferably 15 parts and most preferably 10 parts.

Preferred mixed or shaped polymers for use with branched block ethylene polymers having functionalized amine polymers as reactive thermoplastic polymers include (i) polyolefin resins, (ii) polyamides, (iii) polycarbonates, (iv) hydrogenated polystyrenes. And (v) mixtures thereof. Preferred mixed or shaped polymers for use with branched block ethylene polymers having polyester as the reactive thermoplastic polymer include (i) polycarbonates, (ii) polyesters, (iii) poly (phenylene ethers), (iv) poly Sulfones, (v) polyimides or polyether imides, and (vi) mixtures thereof.

Use of Polyolefin Resins as Mixed or Molded Polymers

Polyolefin resins useful as thermoplastic polymers are polypropylene and one of the ethylene polymers described above in connection with the preparation of branched block ethylene polymers. The production of polypropylene also includes the use of Ziegler catalysts, which results in the formation of isotactic polypropylene by stereoregular polymerization of propylene. The catalyst used is titanium trichloride, usually mixed with aluminum diethyl monochloride, as also described in US Pat. No. 4,177,160 to Cecchin. Various types of polymerization methods used for the production of polypropylene include slurry processes, gas phase and liquid monomer processes performed at about 50-90 ° C. and 0.5-1.5 MPa (5-15 atm), with the removal of amorphous polymers. Special attention should be given to poetry. Ethylene may be added to the reactants to form polypropylene with ethylene blocks.

Various higher olefins may be homopolymerized to form polyolefin resins using Ziegler-Natta catalysts, representative examples of which are 1-butene, 1-methyl-pentene and 4-methyl-1-pentene. Polyolefin resins useful in the present invention also include ethylene / acrylic acid copolymers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, ethylene / carbon monoxide copolymers (including those described in US Pat. Nos. 4,916,208 and 4,929,673). Various ethylene copolymers, such as ethylene / propylene / carbon monoxide copolymers, ethylene / carbon monoxide / acrylic acid copolymers, poly (vinyl chloride) and the like and mixtures thereof. For example, in suspension processes for the production of poly (vinyl chloride), vinyl chloride monomers are copolymerized with other vinyl monomers, such as vinyl acetate, acrylonitrile, butadiene, butyl acrylate, maleic anhydride, olefins or styrenes. To produce a random block or graft copolymer.

A particular advantage of using polyamide resins as molding polymers is that they can be mixed with block terpolymers in the molding machine and avoid the addition of special thermal history to the composition by first extruding pellets of the block terpolymer / molding polymer composition. .

Use of Polyamides as Blending or Molding Polymers

Polyamides useful as thermoplastic polymers are described above as various amine functionalized polymers that can be used in the preparation of block terpolymers. When polyamides are used as molding polymers, different polyamides used to prepare block terpolymers can be used and are often preferred. For example, the polyamide used in the preparation of the block terpolymer may be nylon 6, while the polyamide used as the molding polymer may be nylon 6,6; 6,10 or 12, and / or mixed or shaped polymers may have an average number of amine groups greater than about 2.0 or in a range from about 2.05 to about 3.5. A particular advantage of using polyamide resins as molding polymers is that they can be mixed with block terpolymers in the molding machine and avoid the addition of special thermal history to the composition by first extruding the pellets of the block terpolymers / molding polymer compositions. .

Use of Polycarbonate as Blending or Molding Polymer

Polycarbonates useful as blending or molding polymers include dihydroxy compounds (e.g. bisphenols) and carbonate precursors (e.g. disubstituted carboxylic acid derivatives), haloformates (e.g. bishaloformates of glycol or dihydroxy benzene) Or carbonate esters such as diphenyl carbonate or substituted derivatives thereof. These components are often reacted by a phase interface process in which the dihydroxy compound is dissolved in an aqueous alkaline solution to remove protons to form bisphenolate and the carbonate precursor is dissolved in an organic solvent.

These components are first reacted using a mixture prepared from an aromatic dihydroxy compound, water, and a non-reactive organic solvent that is incompatible with water selected from those in which the carbonate precursor and the polycarbonate product are soluble. Representative solvents include chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, tetrachloroethane, chlorobenzene and chloroform. Caustic soda or other base is then added to the reaction mixture to adjust the pH of the mixture to the level at which the dihydroxy compound is activated in the form of anion.

The carbonate precursor is contacted with a stirred mixture of an aqueous alkali solution of the dihydroxy compound, for which the carbonate precursor can be introduced by bubbling into the reaction mixture in the form of a gas or by dissolving it in the form of a solution. The carbonate precursor is usually used in an amount of about 1.0 to 1.8 mole, preferably about 1.2 to 1.5 mole per mole of dihydroxy compound. The mixture is stirred in a manner sufficient to disperse or suspend the droplets of the solvent containing the carbonate precursor in aqueous alkali solution. The reaction between the organic and aqueous phases produced by this stirring yields the bis (carbonate precursor) ester of the dihydroxy compound. For example, where the carbonate precursor is a carbonyl halide (eg phosgene), the initial phase product of the process is a monochloroformate or dichloroformate or a monomer or oligomer containing fenolate ions at each end.

These intermediates, monocarbonates and oligocarbonates, can be condensed into high molecular weight polycarbonates by dissolving in organic solvents once they are formed and then contacting with coupling catalysts, representative examples of which are tertiary amines such as triethyl amine and dimethyl amino pyridine. Can be.

Upon completion of the polymerization reaction, the organic and aqueous phases are separated to purify the organic phase, from which the polycarbonate product is recovered. The organic phase is washed, if necessary, by centrifugation with dilute base, water and / or dilute acid until the unreacted monomers, residual process chemicals and / or other electrolytes are removed. Recovery of the polycarbonate product may be used for spray drying, steam non-vaporization, direct non-volatile or anti-solvents in a vented extruder (e.g. toluene, cyclohexane, hepic acid, methanol, hexanol or methyl ethyl ketone). By precipitation.

In the melting process for the production of polycarbonates, the aromatic diester of carboxylic acid is condensed with the aromatic dihydroxy compound by transesterification in the presence of a basic catalyst. The reaction is usually carried out at about 250 to 300 ° C. in vacuo under gradual reduced pressure of about 1 to 100 mm Hg.

Polycarbonates also contain carbonate precursors (e.g. phosgene) as aromatic dihydroxy compounds, chlorinated hydrocarbon solvents and substances (e.g. pyridine) for dimethyl aniline or Ca (OH) ₂ which act both as acid acceptors and condensation catalysts. It can be prepared as a homogeneous solution through a process of contacting with a solution.

Examples of dihydroxy compounds suitable for the preparation of polycarbonates are variously bridged, substituted or unsubstituted [Where (I) Z can be wherein (A) all or different moieties are (i) straight, branched, cyclic or acyclic, (ii) aliphatic or aromatic, and (iii) saturated or unsaturated. Divalent radicals consisting of 1 to 35 carbon atoms and up to 5 oxygen, nitrogen, sulfur, phosphorus and / or halogen (eg fluorine, chlorine and / or bromine) atoms, (B) S, S ₂ , SO, SO ₂ , O or CO, or (C) a single bond, and (II) X are each independently hydrogen, halogen (eg fluorine, chlorine and / or bromine), C ₁ -C ₁₂ , preferably C ₁ -C ₈ straight or cyclic alkyl, aryl, alkaryl, aralkyl, alkoxy or aryloxy radicals such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl , Xylyl, phenoxy and / or xyloxyoxy), or a nitro or nitrile radical, and (III) m is 0 or 1] aromatic dihydroxy Compounds (or mixtures thereof).

For example, the bridging radical represented by Z in the above formula may be C ₂ -C ₃₀ alkyl, cycloalkyl, alkylidene or cycloalkylidene, or two or more of these radicals bonded by aromatic or other bonds. Or one or more groups (eg CH ₃ , C ₂ H ₅ , C ₃ H ₇ , nC ₃ H ₇ , iC ₃ H ₇ , cyclohexyl, bicyclo [2.2.1] heptyl, benzyl, CF ₂ , CF ₃ , CCl ₃ , CF ₂ Cl, CN, (CH ₂ ) ₂ COOCH ₃ or PO (OCH ₃ ) ₂ ) may be a carbon atom bonded.

Representative examples of dihydroxy compounds of particular interest are bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, dihydroxydiphenyl and bis (hydroxyphenyl) sulfones, in particular 2,2-bis (4-hydroxyphenyl) propane ("bisphenol-A" or "bis-A"); 2,2-bis (3,5-dihalo-4-hydroxyphenyl) propane ("tetrahalo bisphenol-A"), wherein halogen may be fluorine, chlorine, bromine or iodine [eg, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane ("tetrabromo bisphenol-A" or "TBBA"); 2,2-bis (3,5-dialkyl-4-hydroxyphenyl) propane ("tetraalkyl bisphenol-A"), wherein alkyl may be methyl or ethyl [e.g. 2,2-bis ( 3,5-dimethyl-4-hydroxyphenyl) propane ("tetramethyl bisphenol-A")]; 1,1-bis (4-hydroxyphenyl) -1-phenyl ethane ("bisphenol-AP" or "bis-AP"); Bishydroxy phenyl fluorene and 1,1-bis (4-hydroxyphenyl) cyclohexane.

In general, using a process as described above, values outside these ranges are also acceptable, but have a weight average molecular weight of 8,000 to 200,000 and preferably 15,000 to 40,000, as measured by light scattering or gel permeation chromatography, and / or A polycarbonate product can be obtained having a melt flow value of about 3 to 150, preferably about 10 to 80 (ASTM designation D 1238-89, measured by condition 300 / 1.2). The molecular weight can be adjusted by adding a chain terminator, which may be selected from monofunctional substances such as phenol, carboxylic acid chloride or phenylchlorocarbonate, to the reaction mixture.

The branched polycarbonate molecules, rather than linear, can be obtained by adding trifunctional or polyfunctional monomers (eg, triphenoxy ethane) to the reaction mixture.

A preferred process of the invention is a process in which aromatic polycarbonates are prepared. Aromatic polycarbonates are defined herein in the context of oxygen atoms of one or more dihydroxy compounds present in the polycarbonate chain that are bonded to the carbonyl carbon of the carbonate precursor. In aromatic polycarbonates, all such oxygen atoms are bridged by dihydroxy compound residues, some of which are aromatic rings.

As used herein, the term “polycarbonate” also includes various copolycarbonates, some of which may be prepared by incorporating one or more different dihydroxy compounds into the reaction mixture. When using dicarboxylic acids (eg terephthalic acid or isophthalic acid (or ester forming derivatives thereof)) or hydroxycarboxylic acids in the reaction mixture, or instead of one of the "different" dihydroxy compounds mentioned above, oligomeric prepolymers In order to form, poly (ester / carbonate), which is discussed in more detail in US Pat. No. 4,105,533 (Swart), is obtained.

Copolycarbonates include, for example, carbonate precursors and hydroxy terminated poly (phenylene oxide) or poly (methyl methacrylate) in the presence of one or more dihydroxy compounds and chlorine or amino terminated polysiloxanes. ) Or by reaction with an phosphonyl dichloride or an aromatic ester of phosphonic acid. Siloxane / carbonate block terpolymers are discussed in more detail in US Pat. No. 4,596,970 (Paul).

The methods described above are generally well known for the preparation of carbonate polymers suitable for use in the practice of the present invention, for example several methods are disclosed in US Pat. No. 3,028,365 (Schnell), US Pat. No. 4,529,791 ( Glass) and US Pat. No. 4,677,162 (Grigo).

Use of Polyester as Blending or Molding Polymer

When polyesters are used as mixed or shaped polymers in the mixed compositions of the present invention, the polyesters are as described above as subcomponent (c) in the preparation of the branched block ethylene polymers. Polyesters used as mixed or shaped polymers in the mixed compositions of the present invention preferably have an intrinsic viscosity of at least about 0.85, usefully from about 0.9 to about 1.2, preferably from about 0.95 to about 1.05.

If polyesters are used both as subcomponent (c) of the branched block ethylene polymer and as mixed or molded polymers, it is also preferred that different polyesters are used for each.

Use of Poly (phenylene Ether) as Thermoplastic Polymer

Suitable thermoplastic polymers include poly (phenylene ether) (also known as poly (phenylene oxide)), which are generally polymers comprising a number of structural units described below:

Independently, in each unit, Q ₁ is each independently hydrogen, halogen, primary or secondary C ₁ -C ₈ lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy or halohydrocarbonoxy, Wherein at least two carbon atoms separate halogen and oxygen atoms, and Q ₂ is each independently hydrogen, halogen, primary or secondary C ₁ -C ₈ lower alkyl, phenyl, haloalkyl as defined for Q ₁ , Hydrocarbonoxy or halohydrocarbonoxy. Examples of suitable primary lower alkyl groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and corresponding heptyl groups. Examples of secondary lower alkyl groups are isopropyl, secondary butyl and 3-pentyl. The alkyl radical is preferably straight rather than side chain. Often, Q ₁ is each alkyl or phenyl, especially C ₁ -C ₄ alkyl, and Q ₂ is each hydrogen.

Homopolymer and copolymer poly (phenylene ether) as well as mixtures thereof. Suitable homopolymers are, for example, those containing 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include, for example, random copolymers containing such units together with 2,3,6-trimethyl-1,4-phenylene ether units.

Also included are poly (phenylene ethers) containing moieties that modify properties such as molecular weight, melt viscosity and / or impact strength. Such polymers may be copolymerized by known methods or copolymerized with vinyl monomers such as vinyl nitrile compounds (e.g. acrylonitrile) and vinyl aromatic compounds (e.g. styrene) or polymers such as polystyrene and elastomers. It can manufacture by grafting. The product is usually grafted and contains all of the grafted residues. Another suitable polymer is a coupled poly, wherein the coupling agent reacts with the hydroxy groups of the two poly (phenylene ether) chains in a known manner to produce a high molecular weight polymer containing the reaction product of the hydroxy group and the coupling agent. (Phenylene ether). Examples of coupling agents include low molecular weight polycarbonates, quinones, heterocycles, formals and poly (phenylene sulfides). For example, poly (phenylene ether) / polycarbonate copolymers are known and described in US Pat. No. 5,010,143.

Poly (phenylene ether) usually has a number average molecular weight in the range of about 3,000 to 40,000, and a weight average molecular weight in the range of about 20,000 to 80,000, as measured by gel permeation chromatography. Its intrinsic viscosity is usually in the range of about 0.15 to 0.6, preferably 0.25 dl / g or more when measured in chloroform at 25 ° C. However, values outside this range are also acceptable.

Poly (phenylene ether) is usually prepared by oxidative coupling of one or more corresponding monohydroxyaromatic compounds. Particularly monohydroxy aromatic compound is a useful and easy to manufacture is that the polymer may be characterized as a poly (2,6-dimethyl-1,4-phenylene ether), 2,6-xylenol (wherein, Q ₁ is Each is methyl and Q ₂ is each hydrogen) and 2,3,6-trimethylphenol, wherein each Q ₁ and one Q ₂ is methyl and the other Q ₂ is hydrogen. Various catalyst systems are known for the production of poly (phenylene ether) by oxidative coupling. In most cases they usually contain one or more heavy metal compounds (eg copper, manganese or cobalt compounds) mixed with various other materials. The first group of preferred catalyst systems contain copper compounds, which are described, for example, in US Pat. Nos. 3,306,874, 3,306,875, 3,914,266 and 4,028,341. These are usually mixtures of cuprous or zucchini ions, halide (ie chloride, bromide or iodide) ions and one or more amines. Catalyst systems containing manganese compounds constitute the second preferred group. These are generally alkali systems in which divalent manganese is mixed with anions such as halides, alkoxides or phenoxides. Often, manganese is one or more complexing and / or chelating agents such as dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, w-hydroxyoximes (monomeric And polymeric), o-hydroxyaryl oxime and β-diketone). Known cobalt containing catalyst systems are also useful.

As described above, poly (phenylene ether) is described in more detail in US Pat. No. 4,866,130.

The category of poly (phenylene ether) includes poly (phenylene ether) mixtures prepared by mixing poly (phenylene ether) with polystyrene, vinyl aromatic copolymers and / or other nonstyrene polymers as specified below. Also included. If the thermoplastic polymer used as the blend or molding polymer is a poly (phenylene ether) mixture, the mixture is made from about 20 to about 99 parts by weight, preferably about 30 to 90 parts by weight of poly (phenylene ether) And the remainder are made of polystyrene, vinyl aromatic copolymers and / or non-styrene polymers. Preferred formulations are from about 30 to about 85 parts by weight of poly (phenylene ether) and about 15 to about 70 parts by weight of at least one polystyrene, high impact polystyrene, styrene / butadiene / styrene and / or styrene / ethylenebutylene / styrene block terpolymers It contains one selected from coalescing.

Use of Polysulfones as Blending or Molding Polymers

Polysulfones generally useful as thermoplastic polymers may be described as polymers containing aromatic rings that are para-bonded by partially sulfone groups and partially different groups (eg ether or alkyl groups, but single bonds). However, polysulfones do not contain carbonate [—C (O) —] bonds. Polysulfone is a clear hard thermoplastic resin having a glass transition temperature of about 180 to 250 ° C.

Typically various polysulfones are prepared by nucleophilic substitution of 4,4'-dihalodiphenyl sulfone with bisphenol-A in a bipolar aprotic solvent such as dimethyl sulfoxide or 1-methyl-2-pyrrolidinone. Are manufactured. Fluoride or chloride can be used as the dihalide monomer. In the preparation of polycarbonates, bisphenols are activated in the form of bisphenates in stoichiometric amounts of aqueous bases such as sodium or potassium hydroxide. However, excess water is removed from the system by azeotropic distillation at 120-140 ° C. before the bisphenate is contacted with the dihalo monomer.

The polymerization reaction is then carried out at 130 to 160 ° C. under an inert atmosphere to prevent oxidation of the bisphenate salt. Molecular weights as high as 250,000 can be obtained within 1 hour, and monofunctional halides or phenols can be used as a chain terminator as a result, so that the molecular weight of the polysulfone becomes too high to prevent the viscosity for the process from becoming too high. The highest molecular weight of bisphenol-A polysulfone is obtained when the starting monomer ratio approaches the unit source, and for useful properties its weight (expressed as the reduced viscosity in chloroform at a concentration of 0.2 g / 100 ml at 25 ° C.) is usually 0.4 dl / g or more. Bisphenol-A polysulfone is commercially available from Amoco Performance Products, Inc. as Udel ^TM polysulfone.

Various other polysulfones are synthesized from bisphenols (“bisphenol-S”) which themselves contain sulfone bridges. This polymerization is carried out at higher temperatures (up to about 285 ° C.) in a bipolar aprotic solvent (eg diphenyl sulfone) and uses a base (eg sodium carbonate or potassium carbonate). Removal of water is usually not critical. This type of polymer is commercially available from ICI Americas, Inc. as Victrex ^™ polysulfone.

Other bisphenols used to prepare polysulfones include 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 4,4'-dihydroxydiphenylmethane, hydroquinone, Bis (4-hydroxyphenyl) -2,2-perfluoropropane, bis (4-hydroxydiphenyl) -1,1-cyclohexane, 4,4'-dihydroxybenzophenone and 4,4 ' -Dihydroxydiphenyl.

In general, the repeating units of polysulfones are generally of the formula

-[-Ar--S (O) ₂ --Ar--O--Ar (X) ₄ -[-Z--Ar (X) _4- ] q--O-] p -

Where Ar, D and E are as defined above, q is about 0 to about 3 and p is about 10 to about 100.

Use of Polyimide or Polyetherimide as Blending or Molding Polymer

Polyimides are condensation polymers derived from difunctional carboxylic anhydrides and primary diamines. Two equivalents of water are liberated by the formation of an imide bond, and one equivalent of water is liberated in the formation of the anhydride ring and the second bond by substituting nitrogen in the ring with nitrogen. Polymers can also be prepared by reacting diamines with tetracarboxylic acids directly. In one case, if the starting material is anhydride and two equivalents of water are liberated by heating to form a polymer, an intermediate, for example polyamic acid, is obtained. The reaction of diamines with diamines to form polyamic acid intermediates occurs at ambient temperature in a bipolar aprotic solvent such as dimethylacetamide, cresol or o-chlorophenol. Progress on the final polymer is obtained by heating at 150 to 200 ° C. for 3 to 5 hours to effect cyclodehydation. In the case of using aromatic diamines, accelerators such as triethylamine or acetic acid can be used in the solvents such as chlorobenzene.

Polyimides can also be prepared by reaction of aromatic dianhydrides with aromatic diisocyanates with the removal of carbon dioxide or by reaction of bismaleimides with diamines.

Polyetherimides can be prepared by nucleophilic substitution reactions of bispenoxide salts with dinitrobisimide, or by polyimide formation reactions as described above between diamines and ether bridged dianhydrides. The reaction between the bispenoxide salt and dinitrobisimide is carried out in a bipolar aprotic solvent (eg, dimethylformamide or dimethylsulfoxide mixed with toluene or chlorobenzene) at about 40 ° C. or at 80 to 130 ° C. It can be carried out in N-methylpyrrolidinone in the presence or absence of chlorobenzene. Polyetherimides can also be prepared by substitution reactions of chloro or fluoro groups on bisimides.

Diamines useful for the preparation of polyimides can be aliphatic or aromatic, and several useful groups include m- and p-phenylenediamines, 2,4- and 2,6-diaminotoluene, p- and m-xylylene Diamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminophenyl sulfone, 4,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,3'-dimethylbenzidine, 4,4'-isopropylidenedianiline, 1,4-bis (p-aminophenoxy) benzene, 1,3 -Bis (p-aminophenoxy) benzene, hexa-, hepta-, nona- and decamethylenediamine, 1,4-cyclohexanediamine and bis (4-aminocyclohexyl) methane. Representative dianhydrides useful in the preparation of polyimides include pyromellitic dianhydrides, benzophenone dianhydrides, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydrides, 3,3 ', 4,4'- Biphenyltetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) thioether dianhydride, bisphenol A bisether dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6- Naphthalenetetracarboxylic acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, hydroquinone bisether dianhydride, bis (3,4-dicarboxyphenyl) sulfoxide dianhydride and 3,4,9 , 10-perylene tetracarboxylic acid dianhydride is included.

Bisphenols useful in the preparation of polyetherimides include those described above in connection with the preparation of polycarbonates. Representative dinitrobisimides useful in the preparation of polyetherimides include 1,3-bis (4-nitrophthalimido) benzene, 1,4-bis (4-nitrophthalimido) benzene, 4,4'- Bis (nitrophthalimido) diphenyl ether, 4,4'-bis (4-nitrophthalimido) diphenylmethane, 2,4-bis (4-nitrophthalimido) toluene and 1,6 -Bis (4-nitrophthalimido) hexane.

Process for preparing a mixture of branched block ethylene polymer and blending or molding polymer

The preparation of the compositions of the present invention can be carried out by any suitable mixing device known in the art. Typically, branched block ethylene polymers and thermoplastic mixed or shaped polymer (s) and other components or additives optionally present in the compositions of the invention are tumbled or in powder or particulate form with sufficient agitation to obtain their complete distribution. Dry mix in mixer. If desired, the dry mixed formulation can be applied again under malaxation or shear stress at a temperature sufficient to cause high temperature plasticization in the extruder, for example in the presence or absence of a vacuum. Other devices that can be used in the mixing process include, for example, roller mills, Henschel mixers, ribbon mixers, Banbury mixers or reciprocating screw injection molding machines.

The process for the preparation of the branched block ethylene polymer described above assists in the preferred method of making a mixture of the branched ethylene polymer with the reactive thermoplastic polymer and any mixed or shaped polymer. In the case of using an extruder for the production of branched block ethylene polymers, the separate components and mixed polymers produced are continued through separate inlets during one pass through one extruder for easier handling of the material. Supply. Subsequently, the material subsequently added is usually fed through the bottom inlet of the extruder.

For example, an ethylene polymer can be fed first, followed by an ethylenically unsaturated functionalized organic compound, followed by a reactive thermoplastic polymer, and finally a mixed or molded polymer. Alternatively, the prepared side chain ethylene polymer can be fed first, followed by the reactive thermoplastic polymer, and finally the mixed or molded polymer. Alternatively, the prepared side chain ethylene polymer can be fed together with the reactive thermoplastic polymer and then the mixed or molded polymer can be fed.

Compared to adding a mixed polymer before or concurrently with the reactive thermoplastic polymer in the order of reacting the branched ethylene polymer with the reactive thermoplastic polymer to form the branched block ethylene polymer prior to adding the blending or molding polymer to the mixture, A product with good properties is obtained. These results are obtained because the presence of mixed or shaped polymers can act as a physical barrier to preventing the formation of ethylenically unsaturated functionalized organic compounds into side chains, or can interfere with the reaction of reactive thermoplastic polymers with the formed side chains. .

Process for the manufacture of a product comprising a mixture of branched block ethylene polymers with blended or molded thermoplastic polymer (s)

In the case of softening or melting by application of heat and / or shear, the compositions of the invention are useful in the manufacture and may be compression, injection molding, gas assisted injection molding, calendering, vacuum forming, thermoforming, extrusion and / or Conventional techniques such as blow molding may be used alone or in combination. The compositions may also be molded, spun, or stretched into films, fibers, multilayer laminates or extruded sheets, or may be mixed with one or more organic or inorganic materials on a suitable machine for this purpose.

Incorporation of additional reinforcing impact modifiers in a mixture of branched block ethylene polymers with blends or molding polymers

In another aspect of the invention, a mixture of branched block ethylene polymers with blended or molded thermoplastic polymers may also include reinforcing impact modifiers. Branched block ethylene polymers act effectively as impact modifiers when present in compositions with mixed or shaped polymers, but still perform better in various situations by giving a synergistic effect to the composition between the branched block ethylene polymer and the reinforcing impact modifier. Can be obtained.

Suitable reinforcing impact modifiers include elastomers, such as, for example, A-B or A-B-A copolymers, core-shell grafted copolymers, or mixtures thereof.

AB or ABA copolymers useful as impact modifiers in the present invention may be linear, branched, radial or teleblock, with tapered portions, ie monomers alternated, or transition points between A and B blocks in random order. It may be a diblock ("AB") copolymer, a triblock ("ABA") copolymer, or a radial teleblock copolymer, with or without a portion of the polymer proximate to.

Part A is often prepared by polymerizing one or more vinyl aromatic hydrocarbon monomers (e.g., various styrene-based monomers and substituted groups thereof), having a weight average molecular weight of about 4,000 to about 115,000, having the stability required for processing at elevated temperatures, and softening It has the properties of a thermoplastic having good strength below the temperature at which it becomes. Part B of the copolymer is usually prepared by polymerizing substituted or unsubstituted C ₃ -C ₁₀ dienes, especially conjugated dienes such as butadiene or isoprene, with a weight average molecular weight of about 20,000 to about 450,000 and applied stress It is characterized by an elastomeric property that absorbs and dissipates and then obtains its form again.

In order to reduce oxidative and thermal instability, the A-B or A-B-A copolymers used in the present invention can preferably also be hydrogenated to reduce the degree of unsaturation on the polymer chains and pendant aromatic rings.

Most preferred vinyl aromatic A-B or A-B-A copolymers are vinyl aromatic / conjugated diene block copolymers formed from styrene and butadiene or styrene and isoprene. When the styrene / butadiene copolymers are hydrogenated, they are often represented as styrene / (ethylene / butylene) copolymers in diblock form or as styrene / (ethylene / butylene) / styrene copolymers in triblock form. When the styrene / isoprene copolymers are hydrogenated, they are often represented as styrene / (ethylene / propylene) copolymers in diblock form or as styrene / (ethylene / propylene) / styrene copolymers in triblock form. Vinyl aromatic / diene AB or ABA copolymers as described above are described in US Pat. No. 3,265,766 (Holden), US Pat. No. 3,333,024 (Haefele), US Pat. No. 3,595,942 (Wald) and US Pat. No. 3,651,014 (Witsiepe) It is discussed in more detail in, which is commercially available as various Kraton elastomers from Shell Chemical Company.

Core-shell grafted copolymer elastomers suitable for use as reinforcement impact modifiers herein are based on diene rubbers, alkyl acrylate rubbers, or mixtures thereof, and at least about 45% by weight of the elastomeric or rubber To have a phase. Core-shell grafted copolymers based on diene rubbers contain a substrate latex or core, which polymerizes dienes, preferably conjugated dienes, or dienes and mono-olefins or polar vinyl compounds such as styrene , Alkyl esters of acrylonitrile or unsaturated carboxylic acids (eg methyl methacrylate)]. The substrate latex usually consists of about 40 to 85% diene, preferably conjugated diene and about 15 to 60% mono olefin or polar vinyl compound. The elastomeric core phase should have a glass transition temperature (“Tg”) of less than about 10 ° C., preferably less than about −20 ° C. The mixture of ethylenically unsaturated monomers is then graft polymerized with the substrate latex. Various monomers can be used for this graft reaction, examples of which are: vinyl compounds (eg vinyl toluene or vinyl chloride); Vinyl aromatic compounds such as styrene, alpha-methyl styrene or halogenated styrenes; Acrylonitrile, methacrylonitrile or alpha-halogenated acrylonitrile; C1-C8 alkyl acrylates such as ethyl acrylate or hexyl acrylate; C1-C8 alkyl methacrylates such as methyl methacrylate or hexyl methacrylate; Glycidyl methacrylate; Acrylic acid or methacrylic acid or the like or mixtures of two or more thereof. Preferred grafted monomers include one or more styrenes, acrylonitrile and methyl methacrylate.

The grafted monomers can be added to the reaction mixture simultaneously or sequentially, and when added in turn, a layer, shell or wart-like appendage can be formed around the substrate latex or core. Although only two monomers are used, they are often used in the same amount, but may be added in various ratios with respect to each other. Typical weight ratios for methyl methacrylate / butadiene / styrene copolymer (“MBS” rubber) are about 60 to 80 parts by weight of the substrate latex, about 10 to 20 parts by weight of the first and second monomer shells, respectively. Preferred formulations for MBS rubbers include a core consisting of about 71 parts by weight of butadiene, about 3 parts by weight of styrene, about 4 parts by weight of methyl methacrylate and about 1 part by weight of divinyl benzene; Having a second phase consisting of about 11 parts by weight of styrene and a shell phase consisting of about 11 parts by weight of methyl methacrylate and about 0.1 parts by weight of 1,3-butylene glycol dimethacrylate, wherein the part is used to determine the weight of the total composition It is a standard. As described above, diene-based core-shell graft copolymer elastomers and methods for their preparation are described in US Pat. No. 3,287,443 (Saito), US Pat. No. 3,657,391 (Curfman) and US Pat. No. 4,180,494 (Fromuth). It is discussed in detail.

Core-shell grafted copolymers based on alkyl acrylate rubbers have a first phase forming an elastomeric core and a second phase forming a hard thermoplastic phase for the elastomeric core. The elastomeric core is formed by emulsion or suspension polymerization of monomers of at least about 50% by weight of alkyl and / or aralkyl acrylates having up to 15 carbon atoms, although longer chains may be used, but alkyl is preferably C ₂ -C ₆ , most preferably butyl acrylate. The elastomeric core phase has a T _g of less than about 10 ° C. and preferably less than about 20 ° C. (i) crosslinking monomers having a plurality of addition polymerizable reactive groups all polymerized at substantially the same rate (e.g. butylene diacrylate) and (ii) a number of additions where some are polymerized at rates substantially different from the others About 0.1 to 5% by weight of graft-bonding monomers having polymerizable reactive groups (eg diallyl maleate) are usually polymerized as part of the elastomeric core.

The hard thermoplastic phase of the acrylate rubber is formed on the elastomeric core surface using suspension or emulsion polymerization techniques. The monomers necessary to form this phase together with the required initiator are added directly to the reaction mixture in which the elastomeric core is formed and the polymerization reaction proceeds until the monomer feed is substantially stopped. Glycidyl methacrylate, alkyl esters of unsaturated carboxylic acids such as C ₁ -C ₈ alkyl acrylates (eg methyl acrylate, hydroxy ethyl acrylate or hexyl acrylate) or C ₁ -C ₈ alkyl methacrylates Ethylenically unsaturated monomers, such as methyl methacrylate or hexyl methacrylate] or mixtures thereof are some vinyl monomers that can be used for this purpose. Thermal or redox initiator systems can be used. Due to the presence of the graft binder on the elastomeric core surface, the chain portion consisting of the hard thermoplastic phase is chemically bonded to the elastomeric core. It is preferred that at least about 20% of the hard thermoplastic phase be bonded to the elastomeric core.

Preferred acrylate rubbers consist of about 45 to about 95 weight percent elastomeric core and about 60 to about 5 weight percent hard thermoplastic phase. The elastomeric core may be polymerized from about 75 to about 99.8 weight percent C ₁ -C ₆ acrylate, preferably n-butyl acrylate. The hard thermoplastic phase may be polymerized from at least 50% by weight C ₁ -C ₈ alkyl methacrylate, preferably methyl methacrylate. As described above, acrylate rubbers and methods of making them are discussed in more detail in US Pat. No. 3,808,180 (Owens) and US Pat. No. 4,299,928 (Witman). Are commercially available from a shell grafted copolymer is acrylic Lloyd (Acryloid ^TM) and a para-Lloyd (Paraloid ^TM) of Rohm and Haas (Rohm & Hass) as an elastomer-base variety dienes and acrylate base core.

Other reinforcing impact modifiers or elastomers useful in the compositions of the present invention are generally based on long chain hydrocarbon backbones (“olefinic elastomers”), which can be prepared predominantly from various monoalkenyl or dialkyl monomers. And may be grafted with one or more styrenic monomers. Representative examples of some olefinic elastomers exhibiting changes in sufficient known materials for this purpose are: butyl rubber; Chlorinated polyethylene rubber; Chlorosulfonated polyethylene rubber; Olefin polymers or copolymers such as ethylene / propylene copolymers, ethylene / styrene copolymers or ethylene / propylene / diene copolymers that can be grafted with one or more styrenic monomers; Neoprene rubber; Nitrile rubber; Polybutadiene and polyisoprene.

Examples of preferred olefinic elastomers include (i) one or more olefin monomers (such as ethylene, propylene, isopropylene, butylene or isobutylene) or one or more conjugated dienes (such as butadiene) or mixtures thereof ; copolymers prepared from (ii) ethylenically unsaturated monomers with epoxide groups (eg glycidyl methacrylate) and optionally (iii) ethylenically unsaturated monomers without epoxide groups (eg vinyl acetate) There is.

When a reinforcing impact modifier is used, an amount of about 1 part or more, preferably about 5 parts or more, more preferably about 10 parts or more and most preferably about 15 parts or more (by weight part of the total mixed composition) Usefully exists. The reinforcing impact modifier is usually present in an amount of about 50 parts or less, usefully about 40 parts or less, preferably about 30 parts or less and more preferably about 25 parts or less.

When a reinforcing impact modifier is used with a mixture of a branched block ethylene polymer having a polyester as the reactive thermoplastic polymer component (c) and a thermoplastic resin such as polycarbonate, the reinforcing impact modifier is in parts by weight of the total mixed composition, It is present in the mixture in an amount of about 0.1 to about 25 parts, preferably about 0.5 to about 20 parts, preferably about 1 to about 15 parts, and more preferably about 3 to about 10 parts.

Regarding the use of styrenic copolymers as an additional component of a mixture of branched block ethylene polymers and blends or molding thermoplastic polymers

In embodiments of the invention that are mixtures of branched block ethylene polymers with blended or molded thermoplastic polymers, such mixtures may further comprise styrenic copolymers. The styrene-based copolymers have found particular utility in mixtures of branched block ethylene polymers in which the reactive thermoplastic polymer is polyester.

Suitable styrenic copolymers are prepared from one or more styrene-based monomers and one or more ethylenically unsaturated monomers copolymerizable with the styrene-based monomers. The styrenic copolymers may be random, alternating, block or graft copolymers, and mixtures of one or more styrenic copolymers may also be used.

In addition to styrene itself, styrene-based monomers of particular interest for use in the preparation of styrene-based copolymers include one or more of

[Wherein each A is independently hydrogen, a C ₁ -C ₆ alkyl radical or a halogen atom (eg chlorine or bromine), and each E is independently hydrogen, a C ₁ -C ₁₀ alkyl, cycloalkyl, alkenyl, cyclo Substituted alkenyl or vinyl represented by alkenyl, aryl, alkaryl, aralkyl or alkoxy radicals or halogen atoms such as chlorine or bromine, or two E's may be joined to form a naphthalene structure. Aromatic compounds are included (the literature for "styrene" as comonomer of component (c) can be seen as a reference to the styrenic or vinyl aromatic monomers described in the present invention or other similar classes). Representative examples of suitable styrene-based monomers include, in addition to styrene itself, one or more of the following groups: ring-substituted alkyl styrenes such as vinyl toluene, o-ethylstyrene, p-ethylstyrene, ar- (tert butyl) styrene , 2,4-dimethylstyrene); Ring substituted halostyrenes such as o-chlorostyrene, p-chlorostyrene, o-bromostyrene, 2,4-dichlorostyrene; Ring-alkyl, ring-halo substituted styrenes such as 2-chloro-4-methylstyrene and 2,6-dichloro-4-methylstyrene; Ar-methoxy styrene, vinyl naphthalene or anthracene, p-diisopropylbenzene, divinylbenzene, vinylxylene, alpha-methylstyrene and alpha-methylvinyltoluene.

Ethylenically unsaturated monomers of particular interest for copolymerization with styrene monomers include one or more of the following formulas D--CH == C (D)-(CH ₂ ) _n --G, wherein D is each independently, Represents a substituent selected from the group consisting of hydrogen, halogen (e.g. fluorine, chlorine or bromine), C ₁ -C ₆ alkyl and alkoxy, or together represent an anhydride bond, G is hydrogen, vinyl, C ₁ -C ₁₂ alkyl , Cycloalkyl, alkenyl, cycloalkenyl, alkaryl, arylalkyl, alkoxy, aryloxy, methoxy, halogen (eg fluorine, chlorine or bromine), cyano or pyridyl, n is 0 to 9 Are included.

Representative examples of ethylenically unsaturated monomers that may be copolymerized with styrene-based monomers include those having polar or electronegative groups, and include one or more of the following groups: vinyl nitrile compounds such as acrylonitrile, methacrylonitrile, Ethacrylonitrile, alphachloroacrylonitrile and fumaronitrile); Dienes [e.g. butadiene, isoprene, isobutylene, piperylene, cyclopentadiene, natural rubber, chlorinated rubber, 1,2-hexadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3 -1,3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene, 1,3- and 2,4-hexadiene, chloro- and bromo Substituted butadienes such as dichlorobutadiene, bromobutadiene, chloroprene and dibromobutadiene and butadiene / isoprene and isoprene / isobutylene copolymers; 1,3-divinylbenzene; 2-phenyl propene; C ₂ -C ₁₀ alkylene compounds (eg vinyl or vinylidine chloride) including halo substituted derivatives thereof; α, β-ethylenically unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid, maleic acid, succinic acid, acotinic acid and itaconic acid) and their anhydrides and C ₁ -C ₁₀ alkyl, aminoalkyl and hydroxyalkyl esters and amides (E.g. methyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, methyl α-chloro acrylate, methyl, ethyl or isobutyl methacrylate, hydroxyethyl and hydroxypropyl acrylate, aminoethyl acrylate And alkyl acrylates and methacrylates, such as glycidyl methacrylate); Maleic anhydride; Alkyl or aryl maleates or fumarates (eg diethylchloromaleate or diethyl fumarate); Aliphatic or aromatic maleimide (eg, N-phenyl maleimide, including the reaction product of C ₁ -C ₁₀ alkyl or C ₆ -C ₁₄ aryl primary amines with maleic anhydride); Methacrylamide, acrylamide or N, N-diethyl acrylamide; Vinyl ketones such as methyl vinyl ketone or methyl isopropenyl ketone; Vinyl or allyl acetate and higher alkyl or aryl vinyl or allyl esters; Vinyl alcohol; Vinyl ethers such as C ₁ -C ₆ alkyl vinyl ethers and alkyl substituted halo derivatives thereof; Vinyl pyridine; Vinyl furan; Vinyl aldehydes such as acrolein or crotonaldehyde; Vinyl carbazole; Vinyl pyrrolidone; N-vinylphthalimide. In addition, oxazoline compounds include groups of the formula wherein J are each independently hydrogen, halogen, a C ₁ -C ₁₀ alkyl radical or a C ₆ -C ₁₄ aryl radical, and the like.

(Not provided at filing-Original page 73)

Examples of preferred styrenic copolymers include vinyl aromatic / vinyl nitrile copolymers (e.g. styrene / acrylonitrile copolymers ("SAN")), styrene / maleic anhydride copolymers, styrene / glycidyl methacrylate copolymers , Aryl maleimide / vinyl nitrile / diene / styrene copolymer, styrene / alkyl methacrylate copolymer, styrene / alkyl methacrylate / glycidyl methacrylate copolymer, styrene / butyl acrylate copolymer, methyl meta Acrylate / acrylonitrile / butadiene / styrene copolymers or rubber modified vinyl aromatic / vinyl nitrile copolymers such as ABS, AES or ASA copolymers.

ABS (acrylonitrile / butadiene / styrene copolymer) is an elastomeric-thermoplastic composite in which a vinyl aromatic / vinyl nitrile copolymer is grafted onto a polybutadiene substrate latex. The polybutadiene forms-rubber particles-rubber modifiers or elastomeric components dispersed as discrete phases in the thermoplastic matrix formed by the random vinyl aromatic / vinyl nitrile copolymer. Typically, vinyl aromatic / vinyl nitrile copolymers are contained within and grafted into rubber particles. The AES (acrylonitrile / EPDM / styrene) copolymer is a rubber modified vinyl aromatic / vinyl nitrile copolymer as the vinyl aromatic / vinyl nitrile copolymer is grafted onto a substrate made of EPDM (ethylene / propylene / unconjugated diene) rubber. Styrenic copolymer obtained when AES copolymers are discussed in more detail in US Pat. No. 4,766,175 to Henton. The vinyl aromatic / vinyl nitrile copolymer is a rubber, as is the case for ASA (acrylonitrile / styrene / acrylate) copolymers that are crosslinked with alkyl acrylate elastomers and are discussed in more detail in US Pat. No. 3,944,631 (Yu). Modified styrenic copolymers may also be formed.

The monomers copolymerized to form the styrenic copolymer may each be used in an amount of actually 1 to 99% by weight, but the styrenic copolymer is usually at least about 15% by weight, preferably at least about 35% by weight and more preferably Contains at least about 60% by weight of styrene-based monomers, with the remainder consisting of one or more copolymerizable ethylenically unsaturated monomers. When rubber modified, the styrenic copolymer usually contains at least about 15% by weight, preferably at least about 25% by weight and more preferably at least about 35% by weight of styrene monomer, the remainder being at least one copolymerizable ethylene It consists of a series unsaturated monomer.

The elastomeric phase of the rubber modified styrenic copolymers as used in the compositions of the present invention is up to about 45% by weight, preferably about 5 to 40% by weight and more preferably about 10 to 35% by weight of the copolymer. to be. Preferred elastomeric phases are less than 0 ° C, more preferably less than -30 ° C and most preferably about-when the glass transition temperature (T _g ) is generally measured by ASTM D-746-52T or -56T. 110 to about -50 ° C. The elastomeric phase advantageously has an average particle size of about 10 μm or less, preferably about 0.05 to about 5 μm, more preferably about 0.1 to about 0.3 μm, and the intrinsic viscosity is usually measured in toluene at 25 ° C. In the case of about 0.1 to about 5. In addition to the monomeric components mentioned above, the elastomeric phase is also relatively small, usually less than about 2% by weight of the crosslinking agent, such as divinylbenzene, diallyl maleate, ethylene glycol dimethacrylate, etc., based on rubber. However, such crosslinking should not eliminate the desirable elastomeric properties of the rubber.

The molecular weight of the styrene-based copolymer is not particularly limited as long as its melt flow viscosity can be melt mixed with other components of the composition of the present invention. However, preferably, the melt flow viscosity of the styrenic copolymers measured by ASTM D-1238-65T (1) is about 0.01 to about 10 kPa / min, more preferably about 0.1 to about 5 kPa / min And most preferably about 2 to about 3 dl / min. When the ethylenically unsaturated monomer has a polar group, the polar group usually has a group moment of about 1.4 to 4.4 Debye units, although values outside this range are also acceptable. Styrene-based copolymers can be prepared by emulsion, suspension or mass (bulk) polymerization.

As described above, methods for preparing ABS or other styrene-based copolymers are described in US Pat. No. 2,820,773 (Childers), US Pat. No. 3,238,275 (Calvert), US Pat. No. 3,515,692 (Carrock), US Pat. No. 4,151,128 ( Ackerman, U.S. Patent 4,187,260 (Kruse), U.S. Patent 4,252,911 (Simon), U.S. Patent 4,526,926 (Weber), U.S. Patent 4,163,762 (Rudd) and U.S. Patent 4,624,986 (Weber) Are discussed.

The styrenic copolymer (if present) in the blend of blended or molded thermoplastic polymer and branched block ethylene polymer, if present, is from about 5 to about 75 parts by weight, preferably from about 10 to about 55 parts by weight, preferably about 15 to about 50 parts by weight and more preferably about 20 to about 45 parts by weight.

Regarding the presence of flow modifiers on mixtures of branched block ethylene polymers and blended or molded thermoplastic polymers

Mixtures of branched block ethylene polymers and blended or molded thermoplastic polymers may advantageously also include flow modifiers. Examples of flow modifiers are polyamides and / or polyolefins.

Polyamides useful as flow modifiers are as described above for amine functionalized polymers useful as reactive thermoplastic polymers which are the subcomponent (c) of the branched block ethylene polymers of the invention. Polyolefins useful as flow modifiers are as described above for possible compositions of thermoplastic blends or molding polymers.

The flow modifier resin (if present) in the blend of blended or molded thermoplastic polymer and branched block ethylene polymer, if present, is at least about 5 parts by weight, preferably at least about 10 parts by weight, based on the total weight of the mixed composition. Preferably at least about 15 parts by weight and more preferably at least about 20 parts by weight. Likewise, the flow modifier resin is present in an amount of about 75 parts by weight or less, usefully about 55 parts by weight or less, preferably about 50 parts by weight or less and more preferably about 45 parts by weight or less.

Preferred compositions using branched block ethylene polymers wherein the reactive thermoplastic polymer of subcomponent (c) is polyester:

Preferred compositions using branched block ethylene polymers wherein the reactive thermoplastic polymer of subcomponent (c) is a polyester include:

(a) branched block ethylene polymers : about 1 to about 40 parts, usefully about 2 to about 30 parts and preferably about 5 to about 20 parts;

(b) thermoplastic blends or shaped polymers : about 60 to about 99 parts, preferably about 70 to about 98 parts and preferably about 80 to about 95 parts;

(c) styrenic copolymer (if present) : about 5 to about 75 parts, preferably about 10 to about 55 parts, preferably about 15 to about 50 parts and more preferably about 20 to about 45 parts part;

(d) reinforcing impact modifier (if present) : about 0.1 to about 25 parts, usefully about 0.5 to about 20 parts, preferably about 1 to about 15 parts and more preferably about 3 to about 10 parts And

(e) flow modifier resin (if present) : about 5 to about 75 parts, usefully about 10 to about 55 parts, preferably about 15 to about 50 parts and more preferably about 20 to about 45 parts .

Special Embodiments in which the reactive thermoplastic polymer is polycaprolactone

In one particular aspect of the invention, the branched block ethylene polymer comprises a branched block ethylene polymer wherein the reactive thermoplastic polymer is polycaprolactone. The compositions are found to be useful when mixed with polycarbonate and homogeneous ethylene polymers as mixed or molded polymers and styrene-acrylonitrile grafted ethylene-propylene-diene rubbers as reinforcing impact modifiers. The mixture comprises 0.001 to 50% by weight of branched block ethylene polymer, 0.01 to 50% by weight homogeneous ethylene polymer, 50 to 99.99% by weight polycarbonate and 0.001 to 10% by weight of styrene-acrylonitrile grafted ethylene- Propylene-diene rubber.

The compositions have good melt processability and stiffness and make them useful for profile extrusion, injection molding applications for automotive applications, computers and office equipment and communication devices, and other thin film injection molding applications.

With regard to the presence of additives for the branched block ethylene polymer and / or the branched block ethylene polymer and additional blends or blends of the molding polymer:

Various additives are usefully optionally used to improve the flame retardant or ignition resistance of the compositions of the present invention. Representative examples include oxides and halides of metals of groups IVA and VA of the periodic table [e.g., oxides and halides of antimony, bismuth, arsenic, tin and lead (e.g. antimony oxide, antimony chloride, antimony oxychloride, tin oxide, tin tin) And arsenic oxide)]; Organic and inorganic compounds of phosphorus, nitrogen, boron and sulfur, such as aromatic phosphates and phosphonates (including their halogenated derivatives), alkyl acid phosphates, tributoxyethyl phosphate, 1,3-dichloro-2-propanol phosphate, 3, 9-tribromoneopentoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro (5.5) undecane-3,9-dioxide, phosphine oxide, ammonium phosphate, zinc borate, thiourea , Urea, ammonium sulfamate, poly ammonium phosphate and tin sulfide); Oxides, halides and hydrates of other metals such as titanium, vanadium, chromium and manganese such as titanium dioxide, chromium bromide, zirconium oxide, ammonium molybdate and tin oxide hydrates; Antimony compounds such as antimony phosphate, sodium antimonate, KSb (OH) ₆ , NH ₄ SbF ₆ and SbS ₃ ); Antimony esters of inorganic acids, cyclic alkyl antimonite esters and aryl antimonic acid compounds such as potassium antimony tartrate, antimony salt of caproic acid, Sb (OCH ₂ CH ₃ ), Sb [OCH (CH ₃ ) CH ₂ CH _{3 3} , antimony polyethylene glycorate, pentaerythritol, antimonite and triphenyl antimony); Boric acid; Alumina trihydrate; Ammonium fluoroborate; Molybdenum oxide; Halogenated hydrocarbons such as hexabromocyclodecane; Decabromodiphenyl oxide; 1,2-bis (2,4,6-tribromophenoxy) ethane; Halogenated carbonate oligomers (such as those prepared from tetrabromobisphenol-A); Halogenated epoxy resins such as brominated glycidyl ethers; Tetrabromo phthalic anhydride; Fluorinated olefin polymers or copolymers such as poly (tetrafluoroethylene); Octabromodiphenyl oxide; Ammonium bromide; Isopropyl di (4-aminobenzoyl) isostearoyl titanate; And metal salts of aromatic sulfur compounds such as sulfates, bissulfates, sulfonates, sulfonamides and sulfimides; Other alkali metal and alkaline earth metal salts of sulfur, phosphorus and nitrogen compounds; US Pat. No. 4,786,686 to Laughner and mixtures thereof. Preferred flame retardant additives are antimony trioxide (Sb ₂ O ₃ ). When a flame retardant is used in the composition of the present invention, it is usually about 15% by weight or less, preferably about 0.01 to 15% by weight, preferably about 0.1 to 10% by weight and more preferably based on the weight of the total composition. Preferably in an amount of about 0.5 to 5% by weight.

Various additives are optionally usefully used in the compositions of the present invention for other purposes, such as: antibacterial agents such as organometallics, isoftazolones, organosulfurs and mercaptans; Antioxidants such as phenolic compounds, secondary amines, phosphites and thioesters; Antistatic agents such as quaternary ammonium compounds, amines and ethoxylated, propoxylated or glycerol compounds; Fillers and reinforcing agents such as talc, clay, mica, silica, quartz, kaolin, aluminum nitride, TiO ₂ , calcium sulfate, B ₂ O ₃ , alumina, glass flakes, beads, whiskers or filaments, nickel powders and metals or graphite fiber); Hydrolysis stabilizers; Lubricants such as fatty acids, fatty alcohols, esters, fatty amides, metallic stearates, paraffinic and microcrystalline waxes, silicones and orthophosphoric acid esters; Release agents (eg, complex esters such as particulate or powdered solids, soaps, waxes, silicones, polyglycols, and trimethylolpropane tristearate or pentaerythritol tetrastearate); Pigments, dyes and colorants; Plasticizers such as esters of monohydric alcohols with dibasic acids (or their anhydrides) such as o-phthalates, adipates and benzoates; Heat stabilizers such as organic tin mercaptite, octyl esters of thioglycolic acid and barium or cadmium carboxylates; UV light stabilizers such as hindered amines, o-hydroxy-phenylbenzotriazoles, 2-hydroxy-4-alkoxybenzophenones, salicylates, cyanoacrylates, nickel chelates and benzylidene malonates and jade Salanilide). Preferred hindered phenolic antioxidants are Irganox ^™ 1076 (Ciba-Geigy Corp.). Such additives, when used, usually do not exceed 45% by weight, based on the weight of the total composition, and are usefully about 0.001 to 15% by weight, preferably about 0.01 to 10% by weight and more preferably Is about 0.1 to 10% by weight.

In the case of a mixture of branched block ethylene polymers and additional modified or mixed polymers, the polymer mixture may likewise optionally comprise other additives such as fillers, colorants, antioxidants, antistatic agents, slip agents, tackifiers and fragrances. .

Regarding the use of branched block ethylene polymers to improve the use temperature

The branched block ethylene polymers of the present invention include ethylene polymers that are relatively soft fragments and reactive thermoplastic polymers that are relatively hard fragments, preferably engineering thermoplastics. The presence of hard engineering thermoplastic resin fragments can extend the upper service temperature of the ethylene polymer. In this embodiment, the engineering thermoplastic impact modifier is preferably less than about 50 wt%, more preferably less than about 40 wt%, most preferably about about based on the total weight of the branched block ethylene polymer of the present invention. It is present in an amount of less than 30% by weight and even more preferably less than about 20% by weight. In these amounts, engineering thermoplastics have been observed to extend the temperature range in which branched block ethylene polymers can be used (preferably not melted or deformed). The amount of ethylene copolymer is preferably at least about 0.01% by weight, more preferably at least about 0.1% by weight, most preferably at least about 1% by weight, even more preferably at least about 10% by weight.

Example

The following examples illustrate the invention but do not limit it. %, Ratios and parts are by weight unless otherwise indicated. While Examples (Ex.) Of the present invention are shown by numbers, Comparative Examples (C.S.), which are not examples of the present invention, are shown by alphabet.

To illustrate the practice of the invention, examples of several preferred embodiments are set forth below, but these examples are not intended to limit the scope of the invention in any way. Some of the particularly preferred properties of the present invention are non-proprietary and therefore can be seen by contrasting the properties of the examples using various control formulations (comparative samples) that are not embodiments of the present invention.

Unless otherwise indicated, in Examples 1-7, the branched block ethylene polymers contained in the compositions of the examples were nylon 6 (weight average molecular weight 22,000, melt index 7) and linear or substantially linear ethylene polymers. (Containing 1% by weight maleic anhydride side chain) are each prepared by dry mixing in the amounts as set out below. The maleic anhydride side chain is formed on the linear or substantially linear ethylene polymer in an amount of 1% by weight, based on the weight of the branched linear or substantially linear ethylene polymer, using a peroxide initiator. The dry mixture of nylon 6 and branched linear or substantially linear ethylene polymer is then melt mixed in a 30 mm Warner & Pfleiderer extruder to react nylon 6 with maleic anhydride side chains. It is added as a final block to form a branched block ethylene polymer. The conditions used for this reactive extrusion are as follows: zone temperature; 150, 200, 250, 250 and 250 ° C .; 250 rpm; 70 to 85% torque and residence time; 30 seconds. The branched block ethylene polymer is passed through an ice water bath, cut into granules and then recovered for mixing with the polyolefin resin.

The blend composition mixes the anhydrous components over a paint stirrer respectively for 5 minutes, and then the dry mixed formulation is the same as used to prepare the branched block ethylene polymer, with the zone temperatures 150, 200, 280, 280 and 280 ° C. Prepared by feeding to a Warner & Player extruder under phosphorus conditions. The extrudate is cooled back into strand form and ground as pellets. The pellets were dried in an air blowing oven at 120 ° C. for 3 hours and then the barrel temperature was 200 ° C. (supply), 250 ° C., 250 ° C. and 255 ° C. (nozzles), the molding temperature was 80 ° F. and the screw speed was 120 rpm. It is used to make test specimens in a 70ton Arburg molding machine.

"Polypropylene" is Profax ^™ 6323 polypropylene (Himont);

“HDPE” is a high density polyethylene having a density of about 0.96 g / cm 3 and an I ₂ melt index (according to ASTM D 1238) of about 10 g / 10 min;

"POE" is an unbranched, substantially linear ethylene polymer, as described above;

"POE-b-MAH" is a substantially linear ethylene polymer containing maleic anhydride side chains as described above;

"B / BEP I" is a branched block ethylene polymer made from 70% substantially linear ethylene polymer and 30% nylon 6 containing maleic anhydride side chain;

"B / BEP II" is a Tafmer ^™ P-0180 ethylene / propylene copolymer, having a density of 0.869 g / cm 3, melt index (I ₂ ) of 4 and linear uniform with maleic anhydride side chains Ethylene polymer (Mitsui Petrochemical) (i) branched block ethylene polymer made from 80% by weight and 20% by weight of nylon 6;

"EP" is the weight percent of linear or substantially linear ethylene polymer present in the mixed composition, whether the ethylene polymer is unbranched, branched, or branched block ethylene polymer.

Nylon 6 is a polyamide (Capron 8207) manufactured by Allied Signal having a melt index of 7 and a molecular weight of 22,000.

EG8200gMAH is a polyolefin elastomer with I ₂ of 5 g / 10 min and grafted with 1% by weight of maleic anhydride.

ENGAGE ^* 8150 is a polyolefin elastomer with The Dow Chemical Company having I ₂ of 0.5 g / 10 min.

The following physical and mechanical property tests were performed for Examples 1-5 and Control Groups A-C, and the results of these tests are also shown in Table I:

Impact resistance ("Izod") is measured at 25 ° C. by the Izod test according to ASTM designation D 256-84 (Method A). The notch has a radius of 10 mils (0.254 mm). Izod results are reported in ft-lb / in.

Impact resistance ["weldline"] is also measured at 25 ° C by Izod test according to ASTM designation D 256-84 (Method A), but for samples formed using butt welds in double door molds. . The sample was not notched and placed in the vise so that the weld was 1 mm above the top surface of the vise jaw. Weld line results are also reported in ft-lb / in, with the exception that Example 5 presents "N.B." indicating that the sample was not broken.

The dart drop impact test ("Dart Drop") is performed by dropping 100 pounds of weight, moving 1/2 "darts over a 1/8" thick test sample at 23 ° C. The weighed dart is freely dropped on the inclined track to impact the sample, which is positioned after the impact on the sample falls onto the aluminum casting substrate with a 0.640 inch hole to receive the dart. The device is a Dynatup model 8250. The sample failed if it showed cracks or perforations on the side where no impact occurred. The result is a pass (no break or perforation by the dart at the point of impact) or failure (when the dart is dropped above the track as shown above from the height needed to generate energy to generate a special amount of energy). Cracks or perforations). The values reported in Table I are "pass" or the maximum amount of energy that a sample expressed in ft-lb / in can be tolerated without failure.

Deflection temperature under load ("D.T.U.L.") is measured according to ASTM designation D 648-82 at 66 psi. The results are reported in ° C.

Bending modulus ("F. modulus") is measured according to ASTM D 790. The results are reported in psi.

Unless otherwise indicated, the substantially linear ethylene polymers used in the examples are [((CH ₃ ) ₄ C ₅ ))-(CH ₃ ) ₂ Si-N- (activated with tris (perfluorophenyl) borane. Prepared according to the technique as set forth in US Pat. No. 5,272,236 via solution polymerization using a tertiary C ₄ H ₉ )] TI (CH ₃ ) ₂ organometallic catalyst. Unless otherwise indicated, all parts and percentages are by weight based on total weight. Unless otherwise indicated, the following test methods are used:

1.Notched Izod Impact (ft-lb / in) ASTM D-256 (at 23 ° C, 0 ° C, -18 ° C, -29 ° C, and -40 ° C)

2. Tension (psi) ASTM D-638

3. Yield (psi) ASTM D-638

4. Elongation (%) ASTM D-638

5. Whitening Index (WI) ASTM E-313

6. Yellow Change Index (YI) ASTM E-313

7. Electronic Tissue Picture of Particle Size (μm) Microtome Molding Test Samples

8. Dynatup ASTM D-3763-86 (at -29 ° C)

Specific aspects

Sample manufacture

All samples are prepared by feeding the polymer to a Warner-Plder ZSK-53 / 5L idling twin screw extruder. After feeding the polymer into the extruder, a mixture of maleic anhydride (MAH) / methyl ethyl ketone (MEK) / LUPERSOL 130 (initiator), each having a weight ratio of 1: 1: 0.032, was passed through the injection nozzle by means of a metering pump Supply to 1. LUPERSOL 130 is 2,5-di (tert-butyl peroxy) hexin-3 manufactured and marketed by Atochem. The extrudate is maintained at a mercury vacuum level of at least 26 inches to facilitate non-volatiles of solvents, unreacted MAH and other contaminants.

Attan ^R resin is a ULDPE ethylene 1-octene resin manufactured and marketed by The Dow Chemical Company. Dowlex ^R is a LLDPE ethylene / 1-octene resin manufactured and marketed by Dow Chemical Company. Tafmer ^R P-0180 resin is an ethylene / propylene copolymer resin manufactured and marketed by Mitsui Petrochemical.

The following materials are used:

Polypropylene grafted with ADMER QF 500A, 1.5% by weight of MAH, manufactured and marketed by Mitsui Petrochemical; The grafted polymer has a melt index of 3.0 g / 10 min and a density of 0.900 g / cm 3 at 230 ° C.

Primacor ^R 3460, a copolymer of ethylene and acrylic acid manufactured and sold by The Dow Chemical Company; This material contains 9.7% by weight acrylic acid monomer and has a melt index of 20 g / 10 min.

Graft modified homogeneous ethylene polymer: This material contains 1.3% by weight of MAH, has a melt index of 0.25 g / 10 min and a density of 0.870 g / cm 3.

Profax ^R 6524: polypropylene manufactured and marketed by Himont; The melt index is 4 g / 10 min at 230 ° C. and the density is 0.9 g / cm 3.

Graft modified homogeneous ethylene polymers (hereinafter referred to as INSITE ^™ technical polymers or ITPs) are prepared according to the methods described in US Pat. No. 4,950,541. The polymer components are dry mixed at a specific weight ratio and then fed to a Warner-Plother ZSK-30 twin screw extruder operating at about 210 ° C. The mixture is prepared in a single extrusion pass.

The injection molded sample has 50 ton Negri- operating at a barrel temperature of 200 to 250 ° C., a barrel pressure of 40 bar, a cold molding temperature of 85 ° F. (29 ° C.), and a residence time of about 12 seconds in the cooling mold. It is manufactured by using Negri-Bossi Injection Molder. Samples are formed into plaques that are 2.5 "x 6.5" x 0.075 ".

Flexural modulus and Izod impact properties (at room temperature and −30 ° C.) are measured for the samples in Table 8, respectively. These properties are important in many applications, for example in automotive parts. Properties are measured according to ASTM D-790 and D-256, respectively.

Ethylene-propylene diene elastomer functionalized with maleic anhydride from Uniroyal Chemical; trade name-ROYALTUF 465A.

Ethylene-propylene elastomer functionalized with maleic anhydride (Exxon Chemical; trade name-Exxelor VA 1801).

Ethylene-propylene elastomer graft modified with maleic anhydride as described above (Mitsui; Tafmer P-0180).

Nylon 1000-1 is a low M _w nylon 6,6 used in the injection molding (manufacturer: Hoechst-Celanese).

Nylon 1200-1 is nylon 6,6 with high M _w used in extrusion (Hoechst-Celanese).

Maleic anhydride grafted ethylene 1-octene copolymer (ITP-g-MAH) prepared by grafting maleic anhydride to ethylene-octene copolymer by reactive extrusion is used in this study. The ethylene-octene copolymer used to prepare ITP-g-MAH is a copolymer prepared by solution polymerization from a single site catalyst of constrained geometry. The final graft copolymer (lot XUR-1567-48562-D4) has a melt index of about 0.5 g / 10 min, a density of 0.87 g / dl and a MAH content of 1 wt% (1% MAH-g-ITP). .

Polybutylene terephthalate (PBT) is Celanex 2002 (0.9 IV) obtained from Celanese.

Acrylic copolymer consisting of methyl methacrylate-butylacrylate-glycidyl methacrylate (MMA / GMA) having a weight ratio of 90: 8: 2.

Test Methods:

The dynamic mechanical properties of the samples are studied using the Rheometric Metric Solids Analyzer RSA-II. Test samples are made in the form of thin films (thickness about 15-20 mils). Samples are measured in the range of −120 ° C. to the maximum possible temperature at which the sample melts or is excessively deformed. The measurements are taken at a 7.0 x 10 ^-4 strain at a frequency of 10 rad / s.

Tensile properties are tested in Instron Series IX Automated Testing System 1.04. The parameters of the test instrument are as follows: sample rate: 18.21 pts / sec; Crosshead speed: 2.00 in / min; Full scale load range: 10.00 (lbs); Humidity: 50%; Temperature: 73 ° F.

Example 1

The composition was dry mixed of ITP-g-MAH (1400 g) and PBT (600 g) and fed at 150, 200, 250, 250 and feed rates providing a 30 mm warner and playler twin screw extruder (250 rpm, 70-85% torque). And five barrel zone temperatures fixed at 250 ° C.). The extrudate is pelletized using a Conair strand cutter. From the results in FIG. 1, it can be seen that the MAH-g-ITP / PBT mixture has a higher use temperature than the control sample, ITP-g-MAH or ITP / PBT mixture. Using kinetic mechanical analysis (solid state, extension), both control samples fail at about 60 ° C., but ITP-g-MAH / PBT is stable below 120 ° C. Rheological comparison is shown in FIG. 2. From the results, it can be seen that ITP-g-MAH / PBT is a thermoplastic elastomer with improved processability and improved similar plastic ("shear thinning") behavior. As shown in FIG. 19, the ITP-g-MAH / PBT mixture also improved tensile properties compared to ITP alone. From the tan (δ) values obtained from the DMS tests of FIGS. 2 and 3, it can be seen that these materials are useful for blow molding and thermoforming applications.

Example 2

The composition is prepared by mixing and melt mixing ITP-g-MAH (133 g) and MMA / GMA acrylic copolymer (57 g) at 230 ° C. in a Haake System 90 torque rheometer for 10 minutes. The resulting mixture is then cooled to ambient temperature and pelletized using a mill. From the RSA results of FIG. 4, it can be seen that the reactive mixture of ITP-g-MAH / (MMA / GMA) has a high use temperature, ie the sample is stable at 110 ° C. or lower.

Although the invention has been described in considerable detail through the foregoing embodiments, such description is for illustrative purposes only and should not be regarded as limiting the invention. Many modifications may be made to the above-described embodiments without departing from the spirit and scope of the invention as described in the following claims.

Examples 3-7

The nylon (example of engineering thermoplastics) modified elastomers described during this study are shown in Table 1. These compositions were dry mixed with MAH modified Engage ^* 8200 (trade name of The Dow Chemical Company) (EG 8200 MAH) and nylon 6, maleic anhydride grafted elastomer, at the specified ratios, and 35 mm warner-play at a speed of 250 rpm. And melt mixed at 260 ° C. in a twin screw extruder. Each extrusion modified elastomer is passed through an ice water bath, cut into granules, and collected for final mixing with the specified polyolefin matrix resin.

4 and 5 show shear rates at 0.1 to 100 rad / sec for substantially linear ethylene elastomer, maleic anhydride grafted substantially linear ethylene elastomer and polyamide modified substantially linear ethylene elastomer. Rheological and tan (δ) properties are compared graphically. 6-9 (190 ° C. & 230 ° C.) show the effect of polyamides at various concentrations in maleic anhydride grafted substantially linear ethylene elastomers on these same rheological and elastic modulus properties. These figures show that the novel nylon modified Engage elastomers have not only a significant increase in shear sensitivity than conventional Egnage ^* polymers (examples of narrowly dispersible ethylene polymers), but also significantly higher melt elasticity (low tan (δ)). Indicates. Note that the slope of the viscosity curve at 190 ° C. (below the melting point of nylon 6) has little change from the slope of the viscosity curve at 230 ° C. (higher than the melting point of nylon 6), which is the expected shift due to higher temperatures. Interesting.

Side Chain Block Ethylene Polymers with Nylon 6 Reactive Thermoplastics Example 3 4 5 6 7 ENG * 8200 / MAH 1800 1700 1600 1500 1400 Nylon 6 200 300 400 500 600 Nylon weight% 10 15 20 25 30

* Ethylene polymer sold by The Dow Chemical Company

The polymers of the invention whose properties are shown in FIGS. 4 to 18 are prepared as in Examples 3 to 7. The polymers of FIGS. 1-2A and 2B are prepared as in Examples 1 and 2.

The tan (δ) values of the branched block ethylene polymers of the present invention are also better than those of homogeneous ethylene polymers or of side chain homogeneous ethylene polymers, as well as significantly higher melt elasticity (high storage modulus) at low shear. It represents. Moreover, the branched block ethylene polymers of the present invention have a corresponding effect on their mixtures with shaped polymers. Such mixed compositions exhibit greater shear sensitivity and greater melt elasticity at lower shear than compositions modified with homogeneous ethylene polymers or branched uniform ethylene polymers.

Examples 8 to 24: Use of branched block ethylene polymers wherein the reactive thermoplastic polymer of subcomponent (c) is an amine functionalized polymer

The branched block ethylene polymers contained in the compositions of Examples 8-24 are ethylene polymers containing nylon 6 (weight average molecular weight 22,000, melt index 7) and maleic anhydride branching sites ("E / MAH polymers"). Are each prepared by dry mixing in the amounts shown below. Maleic anhydride branching sites are formed on the E / MAH polymer in an amount of about 1% by weight based on the weight of the E / MAH polymer using a peroxide initiator. The dry mixture of nylon 6 and E / MAH polymer was melt mixed in a 30 mm warner and player extruder to allow nylon 6 to react with the maleic anhydride branching point, and added to the E / MAH copolymer as a final block to form side chains. It is possible to form block ethylene polymers. The conditions used for this reactive extrusion are as follows: zone temperature; 150, 200, 250, 250 and 250 ° C .; 250 rpm; 40 to 65% torque and residence time; 30 seconds. The branched block ethylene polymer is passed through an ice water bath, cut into granules and then recovered for mixing with the thermoplastic molding polymer.

The final compositions of Examples 8-24 and Control Groups A-I mixed the anhydrous ingredients for 5 minutes on a paint stirrer, respectively, and then the dry mixed formulation was the same as used to prepare the branched block ethylene polymer, except Produced by feeding to a Warner & Player extruder under conditions of a zone temperature of 150, 200, 280, 280 and 280 ° C. The extrudate is cooled back into strand form and ground as pellets. The pellet was dried in an air vent oven at 120 ° C. for 3 hours and then the barrel temperature was 200 ° C. (supply), 250 ° C., 250 ° C. and 255 ° C. (nozzle), the molding temperature was 80 ° F., and the screw speed was 120 rpm. It is used to make test specimens in a 70ton Arberg molding machine.

The formulation contents of Examples 8-13 and Control Groups A-D are shown in parts by weight based on the weight of the total composition in Table II below.

In Table I:

"Polypropylene" is Propax 6323 polypropylene (Himont), having a melt index of about 12 and one of the forms of the polyolefin resin described above as mixed component (b);

“HDPE” is a high density polyethylene, having a density of about 0.96 g / cm 3, an I ₂ melt index (according to ASTM D 1238) of about 35 and one of the forms of the polyolefin resin described above as mixed component (b);

"Ethylene polymer" is a "substantially linear" ethylene polymer having a density of about 0.87 g / cm 3 and containing no maleic anhydride branching point;

"E / MAH copolymer" is a "substantially linear" ethylene polymer having a density of about 0.87 g / cm 3 and containing, as branching point, maleic anhydride in an amount of about 1.0 weight percent;

“Nylon 6” is Carpron 8207 (Allied Signal) having a melt index of about 7 and a weight average molecular weight of about 22,000;

"Side-chain block ethylene polymer I" is a side chain that is made from 70% by weight of E / MAH copolymer (i) and 30% by weight of nylon 6 (ii) with I ₂ of about 0.5 and ethylene polymer "substantially linear". Block ethylene polymers;

"Side-chain block ethylene polymer II" is a tarpmer P-, a linear narrow MWD ethylene polymer containing polypropylene, density 0.869 g / cm 3, I ₂ melt index 4 and maleic anhydride branching point. Branched block ethylene polymer prepared from 80% by weight of 0180 (i) and 20% by weight of nylon 6 (ii);

“% Ethylene polymer” refers to the weight percent of ethylene polymer present in the mixed composition, whether the ethylene polymer does not contain branching points, is in the form of an E / MAH copolymer, or is molded into branched block ethylene polymers.

Examples 8-13 and Controls A-D Contents Control Example A B C D 8 9 10 11 12 13 Polypropylene 2,000 1,500 1,500 1,500 1,600 1,500 1,400 1,500 1,500 HDPE 1,600 Ethylene polymer 500 350 200 E / MAH copolymer 500 Nylon 6 150 Branched Block Ethylene Polymers I 400 500 600 300 400 Branched Block Ethylene Polymers II 500 % Ethylene Polymer 0 25 24.8 17.5 14.0 17.5 21.0 20.4 17.3 19.0

The following physical and mechanical property tests are performed on samples of the compositions of Examples 8-13 and Control Groups A-D, the results of which are shown in Table II.

The rheological index includes the viscosity of the sample measured from rheometric mechanical spectroscopy, where the sample is located between the plates in rotation in a reciprocating manner on the sample side. The sample is heated to a certain temperature above its softening point and the viscosity is measured by the force required to rotate the plate at various frequencies. Table II shows the unitless values obtained as the ratio of the viscosity of the sample at 190 ° C. divided by the viscosity at 100 radians / sec when the plate was rotated at 0.1 radians / sec.

Impact resistance [“Izod”] is measured at 25 ° C. by the Izod test according to ASTM designation D 256-84 (Method A). The notch has a radius of 10 mils (0.254 mm). Izod results are reported in ft-lb / in. Impact resistance ["welding line"] is also measured at 25 ° C by Izod test according to ASTM designation D 256-84 (Method A), but for samples formed using butt welds in double door molds. The sample was not notched and placed in the vise so that the weld was 1 mm above the top surface of the vise jaw. Weld line results are also reported in ft-lb / in, with the exception that Example 5 presents "N.B." indicating that the sample was not broken.

The dart drop impact test (“dart drop”) is performed by dropping 100 pounds of weight at 23 ° C. to move a 1/2 "dart over a round test sample 1/8" thick. The weighed dart is freely dropped onto the inclined track at 8050 in / min to impact the sample, which is positioned on the way down on the aluminum casting substrate. The values reported in Table II are the energy required for the dart to break the sample, expressed in ft-lb / in. Deflection temperature under load ("D.T.U.L.") is measured according to ASTM designation D 648-82 at 66 psi. The results are reported in ° F.

Flexural modulus ("F. modulus") is measured according to ASTM D 790. Results are reported in psi.

Properties of Examples 8-13 and Controls A-D Control Example A B C D 8 9 10 11 12 13 Rheological index 4.9 4.7 5.9 10.4 18.2 25.4 16.5 Izod (ft-lb / in) 0.4 2.0 2.8 1.6 2.4 12.1 15.2 3.2 5.7 10.6 Weld line (ft-lb / in) 7.6 8.0 4.5 2.5 17.3 16.8 22.4 11.8 4 N.B. Dart Drop (In-lb) 65 304 282 230 344 341 314 312 279 237 D.T.U.L., (。 F) 170 140 138 149 142 140 134 Flexural Modulus (kpsi) 159 112 120 155 114 113 104

From the data in Table III, it can be seen that the branched block ethylene polymers are effective in preparing compositions having the desired balance of properties when mixed with shaped polymers (eg polyolefin resins). Higher rheological index values are especially noteworthy because higher values indicate greater shear sensitivity. Larger molecules in this ratio indicate that the material maintains its melt strength at low shear, and small denominators indicate that the material is sheared for easier processing, all of which are usually preferred features. The balance of properties presented for the examples is obtained despite the fact that they each contain less ethylene polymers than control groups A or B. From the data in Table III, a very effective method of using ethylene polymers in a mixed composition is to prepare branched block ethylene polymers (as described herein) and then use branched block ethylene polymers as modifiers with the molding polymer. It can be concluded that it is used to Compared with Control Groups A and B, the Examples have greater surface durability and scratch resistance.

The compositions of Examples 14-18 and Control Group E are prepared in the same manner as the compositions of Examples 8-13 and Control Groups A-D. Formulation contents of Examples 14 to 18 and Control Group E are shown in Table IV below by weight of the total composition by weight. In Table IV, "polypropylene", "E / MAH copolymer" and "branched block ethylene polymer I" are the same as shown in Table II. Branched block ethylene polymers made from polyamides in amounts smaller than branched block ethylene polymers I are used in the compositions of Examples 14-17, but they are shown in Table IV as follows:

"Side chain block ethylene polymer III" is a side chain type made from 90% by weight of "substantially linear" ethylene polymer and 10% by weight of nylon 6 having an I ₂ melt index of about 0.5 and containing a maleic anhydride branching point. Block ethylene polymers;

"Side chain block ethylene polymer IV" is a branched block ethylene made from 85% by weight of "substantially linear" ethylene polymer with a I ₂ melt index of about 0.5 and a maleic anhydride branching point and 15% by weight of nylon 6 A polymer;

"Side-chain block ethylene polymer V" is a branched block ethylene made from 75% by weight of "substantially linear" ethylene polymer having an I ₂ melt index of about 0.5 and a maleic anhydride side chaining point and 25% by weight of nylon 6 Polymer.

Nylon weight percentages are also shown in Table III for each branched block ethylene polymer and each total composition.

Tests for the same physical and mechanical properties as those performed for Examples 7-13 and Control Groups A-D were performed for Examples 14-18 and Control Group E, provided that each branched block ethylene polymer was Melt strength is measured using a pulley / drum type melt tensile tester as described above and measured in cmN. The results of these tests are shown in Table V.

Examples 14-18 and the content of control E Control Example E 14 15 16 17 18 Polypropylene 1,500 1,500 1,500 1,500 1,500 1,500 E / MAH copolymer 500 Branched Block Ethylene Polymers I 500 Branched Block Ethylene Polymers III 500 Branched Block Ethylene Polymers IV 500 Branched Block Ethylene Polymers V 500 Branched Block Ethylene Polymers VI 500 Nylon% in the side chain block ethylene polymer table 0 10 15 20 25 30 % Nylon composition 0 2.5 3.75 5.0 6.25 7.5

(Not provided at time of filing-original page 101)

Examples 14-18 and the content of control E Control Example E 14 15 16 17 18 Izod (ft-lb / in) 2.8 2.5 3.2 8.3 9.7 12.1 Weld line (ft-lb / in) 4.5 5.4 6.8 9.4 9.9 16.8 Dart drop (in-lb) 282 310 310 306 305 341 Rheological index 5.9 11.5 11.4 12.7 14.1 18.2 D.T.U.L., (。 F) 138 144 138 141 144 140 Flexural Modulus (kpsi) 120 105 127 122 124 113 Branched Block Ethylene Polymer Melt Strength (cN) 13.8 22.9 25.9 32.2 45.4 52.2

The results of Examples 14-18 and Control Group E are also to demonstrate the balance of the desirable properties that can be obtained by using branched block ethylene polymers as modifiers in the mixed composition. Within the range in which polyamide is used in the present invention to form the final block of the branched block ethylene polymer, it can be seen that the Izod properties are increased as the amount of polyamide used is increased.

The composition of Example 19 and Control Group F is prepared by the same method as the compositions of Examples 8 to 18 and Control Groups A to E. The composition of Example 20 and Control Group G (while containing side chain block ethylene polymers can be made, but which contain no material) are prepared by simultaneously mixing the components for 12 minutes at 220 ° C. in a Banbury mixer. The contents of the formulations of Examples 19-20 and Control Groups F-G are shown in Table V below by weight, based on the weight of the total composition. In Table V, "polypropylene", "E / MAH copolymer" and "branched block ethylene polymer VI" are the same as in Table III. "Nylon 6" is the same as in Table II. Weight percent nylon is also shown in Table VI as a whole for each composition.

Some of the same physical and mechanical property tests as those performed for Examples 8-18 and Control Groups A-E were performed for Examples 19-20 and Control Groups F-G, with the results of these tests being shown in Table VI. It is also presented in

Contents and Properties of Examples 19 to and Controls F to G Control F Example 19 Control G Example 20 Polypropylene 1,500 1,500 1,500 1,500 E / MAH copolymer 350 350 Nylon 6 150 150 Branched Block Ethylene Polymer VI 500 500 % Nylon composition 7.5 7.5 7.5 7.5 Izod (ft-lb / in) 1.6 12.1 2.0 12.7 Weld line (ft-lb / in) 10.9 16.8 5.7 13.3 Dart drop (in-lb) 320 341 288 314 D.T.U.L., (。 F) 143 140 139 143 Flexural Modulus (kpsi) 112 113 115 117 Mixing Extrusion Extrusion Banbury Banbury

From the results of Examples 19 to 20 and control groups F to G, branched block when a branched ethylene polymer and an amine functionalized polymer such as polyamide were mixed with a molding polymer such as polyolefin resin It can be seen that it is important to perform the mixing under conditions such that the ethylene polymer can be formed from branched ethylene polymers and amine functionalized polymers. These conditions include preparing the branched block ethylene polymer in a separate device and then mixing it with the molding polymer or mixing all three materials in the same device (eg extruder), but the presence of the molding polymer Before interrupting the reaction, the amine functionalized polymer is reacted with the branched ethylene polymer to form a branched block ethylene polymer.

For example, the composition of control group F is a mixture of polypropylene with components from which branched block ethylene polymers can be prepared. However, the preparation of control group F does not produce side chain block ethylene polymers in the mixture with polypropylene because all three components of control group F are dry mixed together and then melt mixed simultaneously in an extruder. When the same component is used in Example 19 to prepare the branched block ethylene polymer, first from the E / MAH branched ethylene polymer and the polyamide, the mixture with the resulting polypropylene has an Izod, weld line and dart drop value. Significantly higher compositions are produced. Even when E / MAH branched ethylene copolymers, polyamides and polyolefin resins are mixed simultaneously in a Banbury mixer at high temperature, high shear conditions, as in Control Group G, the properties of the resulting mixed composition are characterized by Control Group F It is not superior to the properties of and is significantly inferior to that of Example 20, where the preparation of the branched block ethylene polymer is completed before melt mixing with the shaped polymer is carried out.

In general, it can be seen that the branched block ethylene polymers have improved rheological properties compared to the components from which they are made. For example, branched block ethylene polymers exhibit significantly higher viscosities than ethylene polymers or branched ethylene polymers at low shear rates when tested by kinetic mechanical spectroscopy, but their viscosity at high shear is ethylene polymers or side chains. It drops to approximately the same level as exhibited by the type ethylene polymer, thus exhibiting significantly higher shear sensitivity than its precursor. The tan (δ) value of the branched block ethylene polymer is also better than that of the ethylene polymer or the branched ethylene polymer and is not only high but also exhibits significantly higher melt elasticity (high storage modulus) at low shear.

Moreover, branched block ethylene polymers have a corresponding effect on the molding polymer and mixtures thereof. The mixed compositions exhibit higher melt strength and elasticity at lower shear than compositions modified with ethylene polymers or branched ethylene polymers, but such mixtures have sufficient shear to dilute it to essentially the same viscosity as the branched ethylene polymers at high shear Sensitivity is shown. For example, FIG. 20 shows the viscosity at various shear rates for polypropylene mixed with branched block ethylene polymers prepared from various levels of polyamide as ethylene / branched branched copolymers and amine functionalized copolymers. Indicates. Mixtures containing branched block ethylene polymers have a higher viscosity at low shear, but at high shear are diluted to the same extent as mixtures containing only ethylene / branched branched copolymers. 21 shows tan (δ) for the same mixture group, which is the loss modulus divided by the storage modulus. Compositions in which polypropylene is mixed with branched block ethylene polymers instead of only ethylene / branched branched copolymers have lower tan (δ), resulting in higher storage modulus. Higher storage modulus indicates a greater amount of recoverable elasticity. The determination of tan (δ) values is based on known methods, such as those derived from Melt Rheology and Its Role in Plastics Processing, Dealy and Wissbrun, Van Nostrand, 1990.

This improvement in properties is due to the tendency for the branched block ethylene polymers to be dispersed in the mixed composition in such a way that the amine functionalized polymer is dispersed as particles of the branched ethylene polymer as submicron particles of large size uniformity. It is believed to be relevant. In contrast, when the amine functionalized polymer is mixed as a component of a random physical mixture with the branched ethylene polymer without first being formed as a branched block ethylene polymer, the amine functionalized polymer dispersed in the ethylene polymer There is little uniformity in particle size, and the amine functionalized polymer can in this case also be dispersed in the molded polymer matrix resin, regardless of what the ethylene polymer is as large multi micron particles.

In conclusion, in a preferred embodiment, the amine functionalized polymer of the branched block ethylene polymer has at least about 50%, often at least about 65%, frequently at least about 80% and optionally about 90% of the particles in the branched ethylene polymer And at least% in size are dispersed as particles comprised within about 80 to about 120% of the average size of all of the amine functionalized polymer particles dispersed in the branched ethylene polymer particles.

When the amine functionalized polymer of the branched block ethylene polymer is dispersed in the branched ethylene polymer as a group of particles having a very uniformly small size, the branched ethylene polymer particles themselves are smaller and more uniformly distributed within the molded polymer matrix. This results in a composition having excellent elastomeric impact strength. In contrast, where the amine functionalized polymer particles are simply components of a random physical mixture that does not contain branched block ethylene copolymer terpolymers, the branched ethylene polymer particles are larger and / or branched ethylene Groups of polymer particles aggregate to form domains, which behave effectively as if they had larger particles. Thus, in another preferred embodiment, when the branched block ethylene polymer is prepared therefrom, the ratio of the size of the branched ethylene polymer particles to the average size of the dispersed amine functionalized polymer particles is such that It is much lower than the ratio of the size of the branched ethylene polymer particles to the average size of the dispersed amine functionalized polymer particles when the unformed and amine functionalized polymer is simply a component of a random physical mixture.

Correspondingly, the useful effect of the mixed composition forming the branched block ethylene polymer may be lost when excess amine functionalized polymer is used. The value added by the amine functionalized polymer, which forms the final block on the branched block ethylene polymer, is complemented by the free amine functionalized polymer, which is cross-linked, weak and crystalline with increased notch sensitivity of the mixed composition. Domains can be formed.

The compositions of Examples 21-24 and Control Groups H and I are prepared using similar mixing conditions as the compositions of Examples 8-18 and Control Groups A-E. However, the control groups H and I mix all the components capable of forming the branched block ethylene polymer, rather than in turn, so that the branched block ethylene polymer can be prepared, but this is not a representative state. Formulation contents of Examples 21-24 and Control Groups H and I are shown in Table VII below, by weight, based on the weight of the total composition.

In Table VII:

"Polycarbonate" is a bisphenol-A polycarbonate with a melt flow of 10;

"Branched block ethylene polymer VII" is a branched block ethylene polymer made from 70% by weight E / MAH copolymer with I ₂ melt index of 0.37 and 30% by weight of nylon 6;

“Epoxy” is a bisphenol-A / epichlorohydrin epoxy resin (eg, D.E.R. 332 epoxy resin; The Dow Chemical Company);

E.S.O. is an epoxidized soybean oil tackifier;

IR 1076 is an Irganox 1076 stabilizer.

In addition, in Table VI, "nylon 6", "branched block ethylene polymer I" and "E / MAH copolymer" are the same as in Table II. Weight percent E / MAH copolymer is also shown overall for control groups H and I and Examples 16-17.

Some of the same physical and mechanical property tests as those performed for Examples 1-11 and Control Groups A-E are performed for Examples 14-17 and Control Groups H and I. Other test performances are as follows:

Tensile strength at break and elongation at break are measured in accordance with ASTM designation D 638-84.

Gloss measurements are performed on test samples according to ASTM designation D 523-85 using Dr. Lange's reflectometer RB3 from Hunter Assocaiates.

The results of each of these tests are shown in Table VII. N.B. indicates no breakage in the weld seam test.

Examples 21-24 and Control H-I Contents Example 21 Example 21 Control H Example 23 Control I Example 24 Polycarbonate 1850 1850 Nylon 6 1700 1570 1600 1428 Branched Block Ethylene Polymers I 430 572 Branched Block Ethylene Polymers VII 150 150 E / MAH copolymer 300 400 Epoxy 4 E.S.O. 2 2 IR 1076 4 4 % E / MAH copolymer in the composition 15 15 20 20

Properties of Examples 21-24 and Controls H-I Example 21 Example 22 Control H Example 23 Control I Example 24 Izod, ft-lb / in, 23 ℃ 13.7 13.7 6.7 8.2 5.6 7.5 Izod, ft-lb in, 0 ℃ 12.8 13.1 6.6 9.0 6.9 8.9 Izod, ft-lb in, 20 ℃ 11.7 10.6 2.4 2.8 3.6 9.0 Izod, ft-lb in, 30 ℃ 9.6 Weld line, ft-lb / in 3.0 7.0 N.B. N.B. N.B. N.B. 20。 Glossy 18 19 60。 Glossy 69 70 The tensile strength 8030 8791 5828 5602 7001 6619 % Elongation 84 111 41 60 171 189 D.T.U.L., (。 F) 291 288 289 335 299 307 Bending modulus (kpsi) 290 299 205 198 228

From the results of Control Groups H and I and Examples 23 and 24, when used as an impact modifier without being formed into branched block ethylene polymers, the ethylene / MAH copolymer is identical to that of the branched block ethylene polymers. It can be seen that the impact characteristics are not improved to the extent. Ethylene / MAH copolymers have lower viscosity and elasticity than branched block ethylene polymers. In conclusion, when the amine functionalized polymer is used as another mixture component rather than used to make the branched block ethylene polymer, the resulting composition is not characterized by the impact properties at the desired low temperatures, particularly as in the block composition. can not do it.

Examples using branched block ethylene polymers in which the reactive thermoplastic polymer of subcomponent (c) is polyester

The composition of Example 25 is a mixture of branched block ethylene polymers with polycarbonates. The composition of the control group Al is a mixture of three components and polycarbonate from which branched block ethylene polymers can be prepared. However, the preparation of Control Group A does not produce a mixture of the branched block ethylene polymer with the polycarbonate, since all four materials are mixed at the same time. The composition of control group B1 is a mixture of ethylene polymers with polycarbonates (“E / MAH copolymers”) containing only maleic anhydride branching point (“E / MAH copolymer”). The compositions of control groups C1 and D1 are mixtures of polycarbonates of substantially linear ethylene polymers, each containing no branching points. The compositions of control groups E1, F1 and G1 are mixtures of polycarbonates with other types of olefin polymers, respectively.

The branched block ethylene polymer contained in the composition of Example 25 is an "substantially linear" ethylene polymer ("E / MAH copolymer") containing 30% by weight poly (butylene terephthalate) and maleic anhydride side chaining point. 70% by weight of the mixture is prepared by melt mixing in a 30 mm Warner & Player extruder. The maleic anhydride branching point is formed on the "substantially linear" ethylene polymer in an amount of about 1% by weight, based on the weight of the E / MAH polymer, using a peroxide initiator. The conditions used in the preparation of the branched block ethylene polymers are as follows: zone temperature; 150, 200, 250, 250 and 250 ° C .; 250 rpm; 70 to 85% torque and residence time; 30 seconds.

The final compositions of Example 25 and control groups A1 to G1 were mixed with anhydrous ingredients for 5 minutes on a paint stirrer, respectively, and then the dry mixed formulation was the same as that used to prepare the branched block ethylene polymer, but with a short zone temperature It is prepared by feeding to a Warner & Player extruder under the conditions of 150, 200, 280, 280 and 280 ℃. The extrudate is cooled back into strand form and ground as pellets. The pellets are dried for 3 hours in an air draft oven at 120 ° C. and then used to prepare test specimens in a 70 ton Arberg molding machine with a barrel temperature of 280 ° C., a mold temperature of 82 ° C. and a screw speed of 120 rpm.

Formulation contents of Example 25 and control groups A1 to G1 are shown in parts by weight based on the weight of the total composition in Table I below.

In Table I:

"Polycarbonate" is a bisphenol-A polycarbonate having a weight average molecular weight of approximately 28,000;

“Branched block ethylene polymers” are branched block ethylene polymers prepared from “substantially linear” ethylene polymers containing poly (butylene terephthalate) and maleic anhydride branching sites, as described above;

"E / MAH copolymer" is a substantially linear ethylene polymer containing maleic anhydride side chains having an I ₂ melt index of 0.5;

"PBT" is poly (butylene terephthalate);

"POE" is an "substantially linear" ethylene polymer containing no maleic anhydride branching point, having an I ₂ melt index of 0.5;

"ECO" is an ethylene / carbon monoxide copolymer;

“HDPE” is a high density polyethylene having a density of about 0.96 g / cm 3 and an I ₂ melt index (according to ASTM D 1238) of about 10;

"LLDPE" is a linear low density polyethylene having an I ₂ melt index (according to ASTM D 1238) of about 4.

The following tests are performed on Example 25 and control groups A1 to G1, the results of which are also shown in Table I:

Impact resistance is measured at 25 ° C. by the Izod test [“Izod”] according to ASTM designation D 256-84 (Method A). The notch has a radius of 10 mils (0.254 mm). The impact is parallel to the flow line of the plaque where the bar is cut in one sample of each composition and perpendicular to the flow line of the other sample. The Izod result ratio in the case of the impact parallel to the flow line to the Izod result of the impact perpendicular to the flow line is given as a unitless value labeled "Isotropic". The Izod results are then used to measure the ductile / membrane transition temperature (“DBTT”) of each sample. Impact resistance is also measured for samples formed at 25 ° C. by the Izod test (“welding line”) according to ASTM designation D 256-84 (Method A), but using butt welds in double door molds. The sample was not notched and placed in the vise so that the weld was 1 mm above the top surface of the vise jaw. Weld line results are reported in kg-cm / cm.

Contents and Properties of Controls A1 to G1 and Example 25 Control Example 25 A1 B1 C1 D1 E1 F1 G1 Polycarbonate 93 95 93 95 95 95 95 93 Branched Block Ethylene Polymers 7 E / MAH copolymer 4.9 5 PBT 2.1 2.1 POE 4.9 5 ECO 5 HDPE 5 LLDPE 5 Anisotropy .678 .748 .853 .879 .838 .575 .672 .783 DBTT, ℃ -35 -45 -20 -20 -20 -40 -30 -35 Welding line, kg-cm / cm 32 26 17 5 7 29 12 83

From the data in Table IX, it can be seen that the branched block ethylene polymer is effective in preparing a composition having the desired balance of properties when mixed with the molding polymer. Side chain block ethylene polymers of the PC mixture can be prepared, but control group A1 containing non-components has a weld line value much lower than that of Example 25. Other control groups, each containing somewhat different types of olefin polymers, are very good in their respective categories, but in all three categories such as Example 25, none of them has the desired balance. For example, the control groups C1 to E1 all have significant levels of anisotropy, but very low weld line values present a problem. From the data in Table VIII, a very effective method of using the olefin polymer in the mixed composition is to use it to prepare the branched block ethylene polymer (as described herein) and then to the branched block as a mixing modifier with the molding polymer. It can be concluded that ethylene polymer is used.

This improvement in properties is due to the tendency for the branched block ethylene polymers to be dispersed in the mixed composition in such a way that the polyester is dispersed as submicron particles of large size uniformity within the particles of the ethylene / branched branched copolymer. It is believed to be relevant. In contrast, if the polyester is simply formed as a component of a random physical mixture with the ethylene / branched branch copolymer without first forming the branched block ethylene polymer, the polyester dispersed in the ethylene polymer will have a particle size There is little uniformity of, and the polyester can in this case also be dispersed in the molded polymer matrix resin, whatever the ethylene polymer as large multi micron particles.

In conclusion, in a preferred embodiment, the polyester of the branched block ethylene polymer is added to the ethylene / branched branched copolymer at least about 50%, often at least about 65%, frequently at least about 80% and optionally about 90% of the particles. At least% size is dispersed as particles comprised within about 80 to about 120% of the average size of the total polyester particles dispersed within the particles of the ethylene / branched branched copolymer.

When the polyesters of the branched block ethylene polymers are dispersed in the ethylene / branched branched copolymer as a group of particles having a very uniformly small size, the ethylene / branched branched copolymer particles themselves are smaller, and more compact in the molded polymer matrix. It is evenly distributed, resulting in a composition having excellent elastomeric impact strength. In contrast, when the polyester particles are simply components of a random physical mixture that does not involve the formation of a terpolymer, the ethylene / branched branched copolymer particles are larger and / or larger than the ethylene / branched branched copolymer Particle groups aggregate to form domains, which behave effectively as if they were larger particles. Thus, in another preferred embodiment, the ratio of the size of the ethylene / branched branched copolymer particles to the average size of the dispersed polyester particles when the branched block ethylene polymer is prepared therefrom is such that no block copolymer is formed. And much lower than the ratio of the size of the ethylene / branched point copolymer particles to the average size of the dispersed polyester particles, when the polyester is simply a component of a random physical mixture.

The compositions of Examples 26-29 are prepared in a similar manner to the compositions of Example 25. The branched block ethylene polymers used in the compositions of Examples 26-28 were prepared from poly (ethylene terephthalate) with an intrinsic viscosity of 0.59 in the presence of potassium paratolyl sulfimide ("KPTSM") catalyst to Prepared by reaction with an "substantially linear" containing ethylene polymer. Side chain block ethylene polymers prepared with the use of catalysts are more preferred, but polymers made without the catalyst, such as those used in Example 26, are still useful products. The branched block ethylene polymers used in each example are made from 30% by weight of "substantially linear" ethylene polymer and 70% by weight of poly (ethylene terephthalate) containing maleic anhydride branching sites. Each mixed composition is prepared from 93 weight percent polycarbonate and 7 weight percent branched block ethylene polymer. The amount of KPTSM catalyst used in Examples 27-29, expressed in weight parts permillion (ppm) measured relative to the combined weight of the E / MAH copolymer and poly (ethylene terephthalate) from which the branched block ethylene polymer was prepared. This is shown in the following table.

The impact resistance of Examples 26-29 is measured on “weld line” samples formed using butt welds in double door molds at 25 ° C. by the Izod test according to ASTM designation D 256-84 (Method A). The sample was not notched and placed in the vise so that the weld was 1 mm above the top surface of the vise jaw. Izod results for Examples 26-29 report 11 trials of each example composition, with each result for 11 trials classified as “no break”, “partial break” or “membrane break”. do. The bridging breakage of the sample in the following table means the breakage of the sample into two separate pieces, whereas in the partial breakage, the sample is not clearly separated and the main part remains in the hinged state. The Izod numerical value reported for each example is the average of the values for each of the 11 trials, partial break or brittle break. Izod results are reported as ft-lb / in as the standard deviation of Izod values for each group, either partial failure or bridging failure.

Example 26 27 28 29 Quantity of KPTSM (ppm) 0 500 1,000 2,000 No damage sample during 11 trials 3 7 7 7 Sample with partial breakage in 11 trials 5 2 4 4 Sample with brittle break in 11 trials 3 2 0 0 Unnotched Izod (ft-lb / in) 20 20 34 43 Standard Deviation-Izod (ft-lb / in) 13 15 2 One

From the results of Examples 26-29, during the preparation of the branched block ethylene polymer used as the mixing modifier in the compositions of Examples 27-29, it was superior to the branched block ethylene polymer prepared in the absence of catalyst in the presence of KPTSM as catalyst. It can be seen that branched block ethylene polymers are made that contribute to the impact strength of the composition. While the composition of Example 26 exhibits very significant Izod values, the compositions of Examples 27-29 have less brittle breakage and improved performance when higher amounts of KPTSM catalyst are used during the preparation of the branched block ethylene polymers used in the mixture. Represents Izod.

Example 30 Use of Branched Block Ethylene Polymers with Reactive Thermoplastic Polymers

Bisphenol A polycarbonate having a weight average molecular weight of 18,000 g / mole is used as the base resin. The polyolefin phase used is a substantially linear ethylene / 1-octene polymer having a density of 0.88 g / dl and I ₂ of 30 g / 10 min. Ethylene / propylene / unconjugated diene elastomer grafted with styrene / acrylonitrile is obtained under the tradename Royalaltuff 372P20 (SAN-g-EPDM) from Uniroyal Chemical. Poly (caprolactone) (PCL) is available from Union Carbide as Tone P-767.

MAH-g-EO in a 70/30 weight ratio is dry mixed with PCL in a tumbler. The mixture is pelletized using a twin screw extruder idling with a 30 mm warner and player. Extrusion conditions include a screw speed of 245 rpm, barrel temperatures of 190, 260, 160 and 260 ° C, and die temperature of 260 ° C. The following is the resin composition:

Resin composition:

Polycarbonate (80 MFR) Homogeneous Ethylene Polymer (0.88g / dl, 30g / 10min.) PCL-g-EO SAN-g-EPDM Contrast 1 100 Control 2 90 10 Example 1 90 10 Control 3 90 10 Example 2 90 9 One Example 3 90 9 One

Molecular weight analysis: size exclusion chromatograph technique coupled with a UV detector using methylene chloride as solvent and tetrahydrofuran as solvent carrier. Calibration is performed using the LEXAN polycarbonate standard.

Viscosity (Nu): Shear viscosity is measured using a capillary rheometer and a circular die having an internal diameter of 1.27 mm and a dimension of 25.4 mm in length. The use temperature is 270 ° C. The reported value is the viscosity at 80 and 2900 sec ⁻¹ .

Izod impact: Izod impact values are measured for pre-notched samples that are 0.25 mm (10 mils). The test is carried out using a pendulum of 10 ft-lb.

Ductile Brittle Transition Temperature (DBTT): The temperature at which a sample has an Izod impact breakage from ductile to brittle characteristics.

Performance characteristics

Molded PC (Mw) g / mol Viscosity at 80 sec ^-1 Viscosity at 2900 sec ^-1 DBTT Room temperature Contrast 1 18500 191 108 More than 30 2.2 Control 2 18500 152 70 -5 0 Example 1 18700 174 84 -20 8.8 Control 3 19200 100 -20 8.3 Example 2 18800 180 75 -10 9.1 Example 3 18600 163 72 8.8

Claims (35)

Ethylene polymer (a), Ethylenically unsaturated functionalized organic compounds (b) and Branched block ethylene polymer comprising a reactive thermoplastic polymer (c) capable of reacting with an ethylenically unsaturated functionalized organic compound. The branched block ethylene polymer of claim 1, wherein the ethylenically unsaturated functionalized organic compound contains a carbonyl group. The branched block ethylene polymer according to claim 1, wherein the ethylenically unsaturated functionalized organic compound is maleic anhydride. The branched block ethylene polymer of claim 1, wherein the ethylenically unsaturated functionalized organic compound contains an epoxy ring. The branched block ethylene polymer of claim 1, wherein the ethylenically unsaturated functionalized organic compound is oxazoline, amine or alcohol. The method of claim 1 wherein the ethylene polymer (i) the M _w / M _n ratio measured by gel permeation chromatography is less than about 3.0, (ii) has a density of about 0.93 g / cm 3 or less, (iii) the Short Chain Branching Distribution Index is greater than about 30%, (iv) side chain block ethylene polymers, which are homogeneous ethylene polymers having a single melt peak measured by differential scanning calorimetry of -30 to 150 ° C. The method of claim 1 wherein the narrow polydispersity ethylene polymer (i) the melt flow ratio I ₁₀ / I ₂ is at least 5.63, (ii) the molecular weight distribution defined by M _w / M _n is (I ₁₀ / I ₂ ) -4.63 or less, (iii) a linear ethylene polymer having essentially the same I ₂ and M _w / M _n , _wherein the critical shear rate at the onset of surface melt crushing is 90 to 110% of the corresponding value for each substantially linear ethylene polymer; Greater than about 50% (iv) branched block ethylene polymers having a single melting point of about 30 to 150 ° C., measured on a differential scanning calorimeter, wherein the substantially linear ethylene polymers also have an SCBD index greater than 50%. 8. The branched block ethylene polymer of claim 7, wherein the critical shear stress at the onset of total melt fracture of the substantially linear ethylene polymer is greater than about 4 x 10 ⁶ dyne / cm 2. 8. The branched block ethylene polymer of claim 7, wherein the substantially linear ethylene polymer has an average of about 0.01 to about 3 long chain side chains per 1000 total carbon atoms. 9. The linear ethylene of claim 8 wherein the processing index of the substantially linear ethylene polymer is 90 to 110% of the corresponding value for the ethylene polymer with I ₂ , polydispersity and density respectively substantially linear. Branched block ethylene polymer having no more than about 70% of the processing index of the polymer. The branched block ethylene polymer of claim 1, wherein the reactive thermoplastic polymer is an amine functionalized polymer. Missing content The branched block ethylene polymer of claim 1, wherein the reactive thermoplastic polymer is polyester. (1) forming an ethylenically unsaturated functionalized organic compound into the side chain of the ethylene polymer to form a branched ethylene polymer, and then (2) reacting the reactive thermoplastic polymer with the branched ethylene polymer, Ethylene polymer (a), Ethylenically unsaturated functionalized organic compounds (b) and A process for producing a branched block ethylene polymer containing a reactive thermoplastic polymer (c) capable of reacting with an ethylenically unsaturated functionalized organic compound. The method of claim 14 wherein the ethylene polymer, (i) the M _w / M _n ratio measured by gel permeation chromatography is less than about 3.0, (ii) has a density of about 0.93 g / cm 3 or less, (iii) the short chain branched distribution index is greater than about 30%, (iv) A single melt peak measured with a differential scanning calorimeter is a homogeneous ethylene polymer having -30 to 150 ° C. The method of claim 15 wherein the ethylene polymer, (i) the melt flow ratio I ₁₀ / I ₂ is at least 5.63, (ii) the molecular weight distribution defined by M _w / M _n is (I ₁₀ / I ₂ ) -4.63 or less, (iii) the critical shear rate at the onset of surface melt fracture is greater than about 50% of the linear ethylene polymer _where I ₂ and M _w / M _n are essentially the same, (iv) a substantially linear ethylene polymer having an SCBD index greater than 50%. 16. The process of claim 15, wherein the reactive thermoplastic polymer is reacted with the branched ethylene polymer in the presence of a nitrogen-containing organic base and a catalyst selected from alkali metal or alkaline earth metal salts having a pKa of at least 7. The method of claim 15, wherein the catalyst is an amine. The method of claim 15, wherein the catalyst is derived from aromatic sulfimide. The method of claim 15, wherein the catalyst is potassium paratolyl sulfimide. The process according to claim 15, wherein the step of forming the ethylenically unsaturated organic compound into side chains of the ethylene polymer and (2) reacting the reactive thermoplastic polymer with the ethylene polymer are carried out in one pass through one extruder. Side chain block comprising blended or shaped polymer with ethylene polymer (a), ethylenically unsaturated functionalized organic compound (b) and reactive thermoplastic polymer (c) capable of reacting with ethylenically unsaturated functionalized organic compound Blends of ethylene polymers. The method of claim 22 wherein the ethylene polymer, (i) the M _w / M _n ratio measured by gel permeation chromatography is less than about 3.0, (ii) has a density of about 0.93 g / cm 3 or less, (iii) the short chain branched distribution index is greater than about 30%, (iv) Blend, which is a uniform ethylene polymer having a single melt peak measured by differential scanning calorimetry of -30 to 150 ° C. The method of claim 22 wherein the ethylene polymer, (i) the melt flow ratio I ₁₀ / I ₂ is at least 5.63, (ii) the molecular weight distribution defined by M _w / M _n is (I ₁₀ / I ₂ ) -4.63 or less, (iii) a critical shear rate at the onset of surface melt crushing is at least about 50% greater than a linear ethylene polymer having essentially the same I ₂ and M _w / M _n , and (iv) an SCBD index greater than 50%. Blends that are linear ethylene polymers. The blend of claim 22 wherein the thermoplastic blending polymer or molding polymer is selected from the group consisting of polycarbonate, polyester, poly (phenylene ether), polysulfone, polyetherimide, polypropylene and polyethylene. The blend of claim 22, wherein the thermoplastic blending polymer or molding polymer is a substantially linear ethylene polymer. 23. The blend of claim 22 further comprising a styrenic copolymer, an elastomeric impact modifier, a flow aid or a mixture thereof. The blend of claim 22 further comprising one or more oils or fillers. The blend of claim 22 wherein the reactive thermoplastic polymer is nylon 6. The mixture of claim 22 in the form of a molded or extruded product. Adding the ethylenically unsaturated functionalized organic compound to the ethylene polymer to form a branched ethylene polymer and thereafter reacting the reactive thermoplastic polymer with the residue of the ethylenically unsaturated functionalized organic compound (b). Forming the branched block ethylene polymer by (1) and subsequently blending the side chain block ethylene polymer with the thermoplastic molding polymer (2), wherein the thermoplastic molding polymer, ethylene polymer, ethylenically unsaturated functionalized organic A method of making a composition from a compound and a reactive thermoplastic polymer. The method of claim 31 wherein the ethylene polymer, (i) the polydispersity is less than about 3.0, (ii) has a density of about 0.93 g / cm 3 or less, (iii) the short chain branched distribution index is greater than about 30%, (iii) The single melt peak measured with a differential scanning calorimeter is a homogeneous ethylene polymer having -30 to 150 ° C. 32. The process of claim 31, wherein the reactive thermoplastic polymer is reacted with a branched narrow ethylene polymer in the presence of a nitrogen-containing organic base and a catalyst selected from alkali metal or alkaline earth metal salts having a pKa of at least 7. 32. The process of claim 31, wherein the unsaturated functionalized organic compound is formed into side chains of the ethylene polymer (a), the reaction of the reactive thermoplastic polymer with the side chain ethylene polymer (b) and the side chain block ethylene polymer are blended thermoplastic resins Or the process (c) of blending with the molded thermoplastic resin is all performed in one pass through one extruder. 32. The process of claim 31, wherein the branched ethylene polymer and the reactive thermoplastic polymer are fed together into the extruder and through the downstream while the blending or molding resin is equally passed through the extruder.