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WO2006023442A1 - Concentrés de nucléation bêta - Google Patents

Concentrés de nucléation bêta Download PDF

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Publication number
WO2006023442A1
WO2006023442A1 PCT/US2005/028981 US2005028981W WO2006023442A1 WO 2006023442 A1 WO2006023442 A1 WO 2006023442A1 US 2005028981 W US2005028981 W US 2005028981W WO 2006023442 A1 WO2006023442 A1 WO 2006023442A1
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Prior art keywords
beta
sheet
polypropylene
concentrate
nucleating agent
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PCT/US2005/028981
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English (en)
Inventor
Philip Jacoby
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Mayzo Inc
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Mayzo Inc
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Publication date
Priority claimed from US10/919,539 external-priority patent/US20050043447A1/en
Priority claimed from US11/053,519 external-priority patent/US20060177632A1/en
Application filed by Mayzo Inc filed Critical Mayzo Inc
Publication of WO2006023442A1 publication Critical patent/WO2006023442A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C08L2205/242—Beta spherulite nucleating agents

Definitions

  • Beta nucleation concentrates can be added to non- nucleated polymer to form beta spherulites in, for example, extruded sheets, which can then be stretched in at least one direction to produce microporous films or perforated reinforcement grids (geo grids).
  • Crystalline polypropylene (also known as "isotactic polypropylene”) can crystallize in three polymorphic forms: the alpha, beta, and gamma forms. In melt- crystallized material the predominant polymorph is typically the alpha or monoclinic form.
  • the beta or pseudohexagonal form generally occurs at levels of only a few percent, unless certain heterogeneous nuclei are present or the crystallization has occurred in a temperature gradient or in the presence of shearing forces.
  • the gamma or triclinic form is typically only observed in low-molecular weight or stereoblock fractions that have been crystallized at elevated pressures.
  • the alpha form also is also referred to as "alplia-spherulites” or “alpha-crystals.”
  • the beta form is also referred to as “beta-spherulites,” “beta-crystals,” “beta-form spherulites,” or “beta-crystallinity.”
  • Beta-crystals have a melting point that is generally about 10 to about 15 0 C lower than that of alpha-crystals.
  • Beta nucleants can be added to thermoformable thermoplastic resin polypropylene in order to broaden the temperature range over which the sheets can be processed and to prevent sag in the thermoforming oven. See U.S. Patent No. 5,310,584 to Jacoby
  • the beta nucleants can induce microvoiding in the sheet when it is deformed during a thermoforming process. Sheets containing high levels of beta spherulites can generally be tlierrnoformed at lower temperatures than polypropylene sheets formed from alpha nucleated polypropylene or non-nucleated polypropylene since the beta spherulites melt at a lower temperature than the alpha spherulites. This can allows the sheets to soften without excessive sag in the thermoforming oven.
  • Opaque polypropylene films can be produced by stretching an extruded polypropylene sheet containing a filler or a colorant such as talc, clay, calcium carbonate, or TiO2.
  • Beta-crystalline polypropylene can be used to produce opaque films without adding any filler or colorant. Such films owe their opacity to the presence of numerous pores throughout the film that are formed when the extruded sheet is stretched either uniaxially or biaxially in the solid state, below the melting point of the beta crystal phase
  • Opaque, microporous polypropylene films have many applications in such areas as labels, food packaging, tape, battery separators, and breathable films which are used in protective clothing, disposable diaper backsheets, and construction applications such as housewrap and roofing membranes.
  • the porosity generated during the production of the film can lower the film density thereby increasing the surface area of film produced by a given weight of polypropylene.
  • Plastic net structures can also be used as reinforcing grids to stabilize concrete and soil in civil engineering and landfill applications. These plastic net structures generally are either uniaxially or biaxially stretched to provide a highly stable, corrosion resistant construction used for such applications as soil stabilization, veneer stabilization, drainage nets in landfills, and concrete stabilization in roads, bridges, and similar structures. Biaxially oriented polypropylene nets can, for example, be used to reinforce road beds.
  • plastic net structures are formed of a polypropylene homopolymer or a copolymer of propylene with ethylene or butene.
  • the reinforcing material should have minimal creep, so that it does not stretch excessively under load.
  • Polypropylene plastic nets can be particularly suitable for these applications since they are not subject to hydrolysis.
  • the plastic web In order to have minimal creep, the plastic web should have a high modulus and be of sufficient thickness so that it deforms to a minimal extent (i.e., exhibits low creep) when loads are applied to it.
  • Strength and flexibility are generally desired in poly propylene net structures.
  • Such structures are typically formed by a process that involves stretching in one or two directions.
  • the material located at the periphery of the junctions of the machine-direction and cross-machine-direction strands herein referred to as "nodes,” mainly contains a random molecular orientation. These node regions therefore can have undesirably low strength. Moreover the central regions of these nodes tend to be in the form of thick, unoriented humps. These humps can constitute areas of weakness, and areas in which the material is inefficiently used.
  • the junctions of the machine-direction and cross-machine-direction strands bear a considerable amount of the load when the netting is used for its intended function.
  • a beta nucleant masterbatch that can be added to a non- nucleated polypropylene resin to produce an extruded sheet containing high levels of beta crystallinity.
  • this sheet is stretched either monoaxially or biaxially to produce a film, the film has a high level of opacity and microvoiding and a reduced density compared to that of film made from a non-beta nucleated precursor sheet.
  • Also provided herein is a more convenient way for a film producer to incorporate a beta nucleating agent into a non-nucleated polypropylene resin. Accordingly, the transition time that is needed to go from the production of a beta nucleated polypropylene sheet to the production of a non-nucleated polypropylene sheet can be reduced.
  • Beta nucleation agents can be used to impart improved properties in polypropylene materials such as sheets and specialty items, for example, geogrids or oriented films produced from extruded sheets.
  • a convenient way of incorporating beta-nucleating agents into polypropylene used to fabricate an extruded product is through the use of a concentrate.
  • a concentrate is defined as a highly loaded, pelletized polypropylene resin containing a higher concentration of nucleating agent then is desired in the final extruded sheet (product).
  • a concentrate can also contain other additives such as stabilizers, pigments, and processing agents, but generally does not contain additives which significantly nucleate the alpha crystal form of polypropylene.
  • Figure 1 is a schematic diagram showing the formation of a polymer net.
  • Figure 2 illustrates the appearance of the machine-direction oriented sheet.
  • Figure 3 illustrates the appearance of a biaxially oriented sheet.
  • Figure 4 illustrates a beam that is supported at each end and deflected in the middle.
  • Figures 5A and 5B illustrate differential scanning calorimeter (DSC) heating scans during the first and second heating cycles of a sample extruded sheet.
  • Figures 6 A and 6B illustrate DSC heating scans during the first and second heating cycles of a sample sheet.
  • Figures 7A and 7B illustrate the DSC heating scans during the first and second heating cycles of a sample sheet.
  • Figure 8 illustrates the appearance of the biaxially oriented net formed by extruded sheets.
  • Figure 9 illustrates the production of the biaxially oriented film produced from an extruded sheet using the tenter frame process.
  • Figure 10 illustrates the production of a biaxially oriented film from an extruded tube using the double bubble process.
  • the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
  • steps in methods of making and using the disclosed compositions are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • film generally refers to a thin, continuous layer of a substance having a thickness of up to about 0.010 inch.
  • sheet generally refers to a thin, continuous layer of a substance having a thickness of at least about 0.010 inch.
  • beta nucleating agent In order to take advantage of the unique attributes of beta crystalline polypropylene to produce opaque microporous films, one can incorporate a beta nucleating agent into a polypropylene resin.
  • a beta nucleating agent There are a very limited number of commercially available beta nucleated polypropylene resins, and the film producer would have to choose one of these resins.
  • the commercially available beta nucleated polypropylene resin is not the one that is best suited for a particular film application due to its molecular weight or melt viscosity, or because a particular copolymer resin is needed for the application.
  • the nucleant can be difficult to add directly to a non-nucleated resin of choice, since the nucleant is typically a very fine powder which does not mix uniformly with the resin pellets. It can be more convenient to use a beta nucleating agent contained within a pellet masterbatch. This masterbatch can contain a much higher concentration of the beta nucleant than is desired in the final extruded sheet, reinforcement grid, or other product. So, in one aspect, the masterbatch is added at a concentration of a few percent to the non- nucleated resin, before it is extruded into a sheet.
  • the film fabricator is free to choose the best polypropylene resin for the application, and then add the beta nucleant masterbatch to this resin to achieve a high level of beta crystal content in the extruded sheet.
  • a beta nucleant masterbatch By using a beta nucleant masterbatch, a more rapid transition from the production of a beta nucleated sheet to a non-nucleated sheet on the same extruder can be achieved.
  • the polyolefin resin is a resinous polymer containing propylene.
  • the polymer can be a homopolymer of polypropylene, a random or block copolymer of propylene and another ⁇ -olefm or a mixture of ⁇ -olefins, or a blend of a polypropylene homopolymer and a different polyolefin.
  • the ⁇ -olefm can be polyethylene or an ⁇ -olefm having 4 to 12 carbon atoms.
  • the ⁇ -olefm contains 4 to 8 carbon atoms, such as butene-1 or hexene-1.
  • at least about 50 mol% of the copolymer is formed from propylene monomers.
  • the copolymer can contain up to about 50 mol%, for example up to about 40 mol%, of ethylene or an ⁇ -olefm having 4 to 12 carbon atoms, or mixtures thereof.
  • Blends of propylene homopolymers with other polyolefins, such as high density polyethylene, low density polyethylene, or linear low density polyethylene and polybutylene can be used.
  • the melt flow rate (MFR)
  • ASTM-1238 of the polypropylene-based concentrate is generally from about 0.1 to 100 g/10 minutes, for example, from about 0.3 to 50 g/10 minutes.
  • This MFR is great enough for facile and economical production of the extruded sheet, but not so great as to produce a sheet with undesirable physical properties.
  • the MFR can be in the range of from about 0.1 to about 10 decigrams/minute (dg/min), for example, from about 0.25 to 2.5 dg/min.
  • dg/min decigrams/minute
  • the MFR of the resin exceeds about 10 dg/min, disadvantages can be caused by the inability to orient the sheet to the desired draw ratios.
  • the MFR is less than about 0.1 dg/min, difficulties can be encountered in shaping of the sheet due to the high melt viscosity.
  • the beta spherulites are formed through the addition of a beta nucleating agent.
  • a beta nucleating agent H. J. Leugering, M ⁇ kromol. Chem. 109, 204 (1967) and A. Duswalt et al., Amer. Chem. Soc. Div. Org. Coat, 30, No. 2 93 (1970) disclose the use of certain nucleating agents to cause the preferential formation of beta-form spherulites.
  • the structure of the nucleant can induce the formation of crystals with a defined structure.
  • nucleating agents can form beta-spherulites in a more controlled concentration than these nucleation methods
  • the nucleating agent can be any inorganic or organic nucleating agent that can produce beta-spherulites in the melt-formed sheet at a concentration corresponding to a K- value obtained by x-ray diffraction analysis of 0.2 to 0.95.
  • the efficiency of the beta nucleating agent and the concentration of beta spherulites in a polypropylene sample can be measured by the size of the melting endotherm observed in a differential scanning calorimeter (DSC) corresponding to the melting of the beta crystals.
  • DSC differential scanning calorimeter
  • Suitable beta-nucleators include, but are not limited to, the bisodium salt of o-phthalic acid; the aluminum salt of 6-quinizarin sulfonic acid; isophthalic and terephthalic acids; N',N'-dicyclohexyl-2,6-naphthalene dicarboxamide, also known as NJ Star NU-100, developed by the New Japan Chemical Co.; and the gamma-crystalline form of a quinacridone colorant Permanent Red E3B, herein referred to as "Q-dye.”
  • the structural formula for Q-dye is:
  • beta-nucleating agent is disclosed in German Patent DE 3,610,644.
  • This beta-nucleating agent is prepared from two components, (A) an organic dibasic acid, such as pimelic acid, azelaic acid, o-phthalic acid, terephthalic acid, and isophthalic acid; and (B) an oxide, hydroxide or an acid salt of a metal of Group II, such as magnesium, calcium, strontium, and barium.
  • the acid salt of the second component (B) may be derived from an organic or inorganic acid, such as a carbonate or stearate.
  • the composition can contain up to about 5 wt % of Components A and B (based the weight of the polymer) and preferably contains up to about 1 wt % of Components A and B.
  • Materials that preferentially nucleate beta-form spherulites generally do not appreciably nucleate the alpha crystal form of polypropylene.
  • a material that does not appreciably nucleate that alpha crystal form of polypropylene produces polypropylene wherein less than about 5% of the crystallized polypropylene is in the alpha form.
  • the material produces polypropylene wherein less than about 2% of the crystallized polypropylene is in the alpha form.
  • the material produces polypropylene wherein less than about 1% of the crystallized polypropylene is in the alpha form, hi yet another aspect, the material produces polypropylene wherein less than about 0.5% of the crystallized polypropylene is in the alpha form. It is also understood that the amounts of beta-nucleation and alpha-nucleation can vary depending upon the concentration of the nucleant in the polypropylene.
  • the beta nucleating agent is present in the disclosed compositions in a concentration of from about 0.1 ppm to about to 5000 ppm, based upon the total weight of the composition.
  • the beta nucleating agent can be present in a concentration of from about 0.1 ppm to about to 1 ppm, of from about 0.1 ppm to about to 5 ppm, of from about 0.1 ppm to about to 10 ppm, of from about 0.1 ppm to about to 50 ppm, of from about 0.1 ppm to about to 100 ppm, of from about 0.2 ppm to about to 50 ppm, of from about 0.2 ppm to about to 100 ppm, of from about 100 ppm to about to 500 ppm, of from about 500 ppm to about to 5000 ppm, of from about 50 ppm to about to 500 ppm, of from about 200 ppm to about to 1000 ppm, of from about 1000 ppm to about to to
  • the properties of the resulting extruded sheet are dependent on the selection of the beta nucleant and the concentration of the beta nucleant. Suitable concentration ranges for the beta nucleant depend on which beta nucleant is selected. The amount of nucleant depends on the effectiveness of the particular nucleant in inducing beta-crystals and the thermal conditions under which the sheet is produced. The Q-dye can be most effective at very low levels, in the range of from about 0.1 ppm to about 100 ppm.
  • the beta nucleant can be quinacridone colorant Permanent Red E3B and can be present in the composition at a level of from about 0.5 ppm to about 50 ppm, based on the weight of the resinous polymer of propylene.
  • concentrations in the range of from about 200 ppm to about 5000 ppm can be used in order to produce an extruded sheet that has a K value in the desired range.
  • the amount of nucleant can be calculated based on studies using Q-dye. It is understood that other beta-nucleants may have different activities and that different amounts could be required to result in the same amount of nucleation and formation of beta spherulites in the final product.
  • the nucleating agents are typically in the form of powdered solids. To efficiently produce beta-crystallites, the powder particles are generally less than about 5 microns in diameter, for example, no greater than about 1 micron in diameter.
  • the resinous polymer of propylene can be admixed as needed with a variety of additives, including lubricants, antioxidants, ultraviolet absorbers, radiation resistance agents, antiblocking agents, antistatic agents, coloring agents, such as pigments and dyes, opacifiers, such as TiO 2 and carbon black. Standard quantities of the additives can be included in the resin. Care is generally taken to avoid incorporation of other nucleating agents or pigments that act as nucleating agents, since these materials can prevent the proper nucleation of beta-spherulites.
  • Alpha nucleating agents that are generally omitted from the formulation include, but are not limited to, talc, sodium benzoate; lithium benzoate, NA-11 from Atnfine, which is the sodium salt of 2,2 '-methylene bis (4,6-di-tert-butylphenyl) phosphate; and sorbitol clarifiers, such as Millad 3988 from Milliken Chemicals ⁇ i.e., bis(3,4-dimethylbenzylidene) sorbitol). Radical scavengers, such as dihydroxy talcite, are also generally avoided, since they have some nucleating ability.
  • additives that significantly nucleate the alpha crystal form of polypropylene measurably decrease proper nucleation of beta-spherulites.
  • additives that significantly nucleate the alpha crystal form of polypropylene increase the ratio of alpha crystallinity to beta crystallinity by at least about 5%.
  • such additives are absent from the disclosed compositions.
  • such additives are present in an amount that nucleates the alpha crystal form of polypropylene by less than about 5%.
  • Mineral materials used as whiteners or opacifiers such as barium sulfate (BaSO 4 ), titanium dioxide (TiO 2 ), and calcium carbonate (CaCO 3 ), may be added to the resin.
  • the effective amount of such additives can depend upon the particular application or end-use intended for the plastic film and can range from 0.005 to about 5 wt %, based on the weight of the polymer.
  • carbon black can be added to a beta-nucleated resinous polymer of propylene at a level of from about 0.5 to about 5 wt %, based on the weight of the polymer.
  • the beta-nucleating agent can optionally be incorporated into the carbon black concentrate to be added to the resin during the extrusion process.
  • Antistatic agents can include, but are not limited to, alkali metal alkane sulfonates, polyether-modified (i.e., ethoxylated and/or propoxylated) polydiorganosiloxanes, and substantially linear and saturated aliphatic tertiary amines containing a C 1O-20 aliphatic radical and substituted by two C 1-4 hydroxyalkyl groups, such as N,N-bis-(2-hydroxyethyl)-alkyl amines containing C 10-20 , preferably C 12-18 , alkyl groups.
  • Suitable antiblocking agents include inorganic additives, such as silicon dioxide, calcium carbonate, magnesium silicate, aluminum silicate, calcium phosphate; nonionic surfactants; anionic surfactants; and incompatible organic polymers, such as polyamides, polyesters, and polycarbonates.
  • examples of lubricants include higher aliphatic acid amides, higher aliphatic acid esters, waxes, and metal soaps.
  • Additives can interfere with nucleation. For example, high concentrations of carbon black and certain pigments can inhibit nucleation, thereby requiring higher concentrations of nucleants to produce an equivalent amount of nucleation. As used herein, concentrations of nucleants can be calculated based on the amount required in the absence of additives, with the understanding that variation in amounts can be required to adjust for the presence of other additives. Typically, the amount of nucleant can be increased as additives are incorporated into the polypropylene.
  • a convenient way of incorporating beta-nucleating agents into polypropylene used to fabricate an extruded product can be through the use of a concentrate.
  • a concentrate can be defined as a highly loaded, pelletized polypropylene resin containing a higher concentration of nucleating agent than is generally desired in the final extruded sheet (product).
  • the nucleating agent is present in the concentrate in a range of from about 0.005% to about 2.0% (from about 50 ppm to about 20,000 ppm), in a further aspect, in a range of from about 0.0075% to about 1% (from about 75 to about 10,000 ppm).
  • the nucleating agent is present in the concentrate in a range of from 0.0075% to about 0.0500% (from about 75 ppm to about 500 ppm).
  • Typical concentrates can be blended with non-nucleated polypropylene in the range of from about 0.5% to about 50% of the total polypropylene content of the extruded product. In one aspect, the range is from about 1% to about 10% of the total polypropylene content of the extruded product.
  • the concentration range of nucleant in the final extruded sheet product can be from about 0.00005% to about 0.1% (from about 0.5 ppm to about 1000 ppm). As a further example, the concentration can be from about 1 ppm to about 200 ppm.
  • a concentrate can also contain other additives such as stabilizers, pigments, and processing agents, but generally does not contain any additives that significantly nucleate the alpha crystal form of polypropylene.
  • the nucleating agent is present in the concentrate in a range of from about 0.01% to about 2.0% (about 100 to about 20,000 ppm), for example, from about 0.02% to about 1% (about 200 to about 10,000 ppm).
  • the concentration range of nucleant in the final geogrid product can be from about 0.0001% to about 0.1% (about 1 to about 1000 ppm), for example, from about 2 ppm to about 200 ppm.
  • the concentrate can be made from a polyolefin carrier resin.
  • the carrier resin used to make the concentrate can be polypropylene homopolymer, polypropylene copolymers containing other alpha-olefin monomers, or other polyolefins.
  • polypropylene means a polypropylene homopolymer or a polypropylene copolymer containing other alpha-olefin monomers.
  • the melt flow rate of the carrier resin can influence the melting and dispersability of the nucleating agent and is typically equal to or higher than the melt flow rate of the base polypropylene.
  • a concentrate can be made by melt blending the pure nucleating agent with a non-nucleated polypropylene resin using a twin screw extruder or other appropriate mixing device, such as a B anbury mixer.
  • the non-nucleated polypropylene resin can be in either powder or pellet form. If a powder is used, additional stabilizing agents, such as anti ⁇ oxidants, can also be incorporated.
  • One method for making concentrates can be to first prepare a powdered pre-master batch by blending the powdered polypropylene and powdered nucleant in a high intensity mixer, such as a Henschel mixer. This powdered pre- master batch can then be blended with additional non-nucleated polypropylene powder in a twin-screw extruder.
  • a concentrate can also be made using a double-compounded master batch, hi this process, a pelletized single-pigment master batch can be made by extruding a blend of the pure nucleating agent and non-nucleated polypropylene.
  • the nucleating agent can be present in a concentration of from about 10% to about 50% of the total polypropylene content of the concentrate.
  • the single-pigment master batch can then be diluted down a second time with pure polypropylene, for example, to a ratio of 100 to 1, resulting in a concentrate with a nucleant concentration of from about 0.1% to about 0.5% of the total polypropylene content.
  • This second master batch can be further diluted by blending the concentrate with additional non-nucleated polypropylene.
  • the concentrate can be blended with from about 90% to about 95% by weight non-nucleated polypropylene resulting in a concentrate which has been diluted down by a factor of from about 10 to about 20, to a final concentration of nucleant in the concentrate of from about 0.005% to about 0.05% by weight (from about 50 ppm to about 500 ppm).
  • the quinacridone pigment is used as the beta nucleant for the production of microporous oriented polypropylene film
  • the concentrate can contain, for example, from about 50 ppm to about 200 ppm of the beta nucleant.
  • the concentrate can contain, for example, from about 425 ppm to about 550 ppm, or about 450 ppm.
  • Pelletized master batch concentrate can be added into the hopper end of a sheet extruder using a loss-in-weight, gravimetric or volumetric feeder.
  • the hopper also can contain pellets of the non-nucleated polypropylene resin. Additional feeders can be used to incorporate other additives in concentrate form such as carbon black, other pigments and stabilizers.
  • Concentrate containing the nucleating agent can be added to polypropylene to form the final product in an amount of from about 0.5% to about 50% by weight. For example, concentrate can be added in an amount of from about 1% to about 10% by weight.
  • the mixture can then be fed into the feed throat of the extruder and melt blended to form a homogeneous melt.
  • the extruder can be a single or twin-screw extruder. Further, the extruder can optionally contain a static mixer and/or melt pump to further homogenize the blend and control the output rate of the extruder.
  • the method of producing the final uniaxially or biaxially oriented polypropylene film can be achieved via the following steps: (1) Melt forming a polymeric composition that contains a crystalline resinous polymer of propylene containing an effective amount of nucleating agent capable of producing beta spherulites in the solidified sheet. (2) Quenching the melt-formed sheet at a quench temperature sufficient to produce beta-spherulites in the sheet.
  • the resulting sheet has a K- value of ranging from about 0.1 to about 0.95, in another aspect, ranging from about 0.2 to about 0.95.
  • the resulting sheet can show a prominent melting peak for the beta crystal phase when a sample of the sheet is placed in a DSC and heated at a rate of about 10 0 C per minute.(3) Extruding the quenched sheet. (4) Orienting the solid sheet in the machine direction by passing it over a series of heated rollers moving at different speeds at a sufficient temperature to achieve draw ratios ranging from about 2:1 to about 10:1.
  • the drawing can occur as the sheet passes from the slowly rotating roll to the rapidly rotating roll, and the draw ratio can be defined as the ratio of the speed of the fast draw roll to the speed of the slow draw roll.
  • the uniaxially drawn sheet can be heated to a temperature sufficient to orient it in a direction perpendicular to the MD at draw ratios ranging from about 2:1 to about 10:1.
  • the following steps can be performed: (6) Perforating the quenched sheet after extrusion so that it contains a square or rectangular pattern of holes or depressions. (7) Heating the perforated sheet to a temperature sufficient to orient it in the machine (extrusion) direction at draw ratios ranging from 2:1 to 10:1.
  • the uniaxially drawn sheet can be heated to a temperature sufficient to orient it in a direction that is perpendicular to the MD at draw ratios ranging from 2:1 to 10:1.
  • Figure 1 illustrates steps 6 and 7 used in the process for manufacturing the plastic net.
  • An alternative method for producing a biaxially oriented film can be to (8) simultaneously orient the film in two directions by extruding a tubular sheet from an annular die, and then cooling the tube over a mandrel or by spraying water on the tube, and then reheating the tube and applying internal air pressure to re-inflate the tube to form a biaxially oriented bubble, which can then be slit and wound up onto a roll.
  • This "double bubble" process is widely practiced.
  • the beta nucleant concentrate of this invention can be blended into the polypropylene resin used to extrude the tube in the same manner as that used for flat extruded sheet, in order to take advantage of the unique property enhancements deriving from the use of beta nucleation.
  • the sheet can be perforated. After biaxial stretching, the sheet can form a web or grid. In another aspect, the sheet can be unperforated, or solid. After stretching, the sheet can form a film. Although referred to as solid, it is understood that such a sheet containing beta-nucleating agents, when stretched, can undergo microvoiding.
  • Figures 9 and 10 illustrate steps 5 and 8 used in the process for manufacturing an oriented film.
  • An example of the use of tenter frames is disclosed in U. S. Pat. No.
  • the film can be drawn off the chill roller 18 to a stretching section 20 to which the machine direction orientation occurs by means of idler rollers 22 and 23 which lead to preheat rollers 25 and 26.
  • the film As the film is drawn off the chill roller 18 and passed over the idler rollers, it can be cooled to a temperature of from about 30 °C to about 60 ° C. hi stretching the film in the machine direction, it can be heated by preheat rollers 25 and 26 to an incremental temperature increase of from about 60 0 C to about 100 °C and then passed to the slow roller 30 of the longitudinal orienting mechanism.
  • the slow roller may be operated at any suitable speed, in one aspect from about 20 feet per minute to about 40 feet per minute in this type of pilot production line.
  • the fast roller 31 can be operated at a suitable speed, in one aspect about 150 feet per minute, in a pilot line, to provide a surface speed at the circumference of about 4 to about 7 times that of the slow roller in order to orient the film in the machine direction, hi a commercial production line, casting speeds can be much higher, such as from about 20 to about 60 meters per minute. In one aspect, final speeds can be from about 120 to about 360 meters per minute.
  • the oriented film As the oriented film is withdrawn from the fast roller, it can be passed over a roller 33 at room temperature conditions. From here it can be passed over tandem idler rollers 35 and 36 to a lateral stretching section 40 where the film can be oriented by stretching in the transverse direction.
  • the section 40 includes a preheat section 42 comprising a plurality of tandem heating rollers (not shown) where it can be again reheated to a temperature within the range of from about 90 0 C to about 140 °C. From the preheat section 42 of the tenter frame, the film can be passed to a stretching or draw section 44 where it can be progressively stretched by means of tenter clips (not shown) which grasp the opposed sides of the film and progressively stretch it laterally until it reaches its maximum lateral dimension.
  • Lateral stretching ratios are typically greater than machine direction stretch ratios and often range anywhere from 3-12 times the original width. In one aspect, ratios of from about 5 to about 10 times are usually preferred.
  • the concluding portion of the lateral stretching phase includes an annealing section 46, such as an oven housing, where the film can be heated at a temperature within the range of from about 120 °C to about 170 0 C for a suitable period in time, in one aspect, from about 1 to about 10 seconds.
  • the annealing time helps control certain properties, and increased annealing is often specifically used to reduce shrinkage.
  • the biaxially oriented film can then be withdrawn from the tenter frame and passed over a chill roller 48 where it can be reduced to a temperature of, in one aspect, less than about 50 0 C and then applied to take-up spools on a take-up mechanism 50.
  • the initial orientation in the machine direction can be carried out at a somewhat lower temperature than the orientation in the lateral dimension.
  • the film exiting the preheat rollers can be stretched in the machine direction at a temperature of about 120 0 C.
  • the film can be cooled to a temperature of about 50 °C and thereafter heated to a temperature of about 160 °C before it is subject to the progressive lateral dimension orientation in the tenter section.
  • the double-bubble process is described in U.S. Pat. No. 3,555,604 to Pahlke and incorporated herein by reference.
  • FIG. 10 illustrates the major components of such a double bubble processing line.
  • the plastic feedstock 10 can be fed into extruder 12.
  • a primary bubble 120 can form by inflating the bubble as the melt exits die 122.
  • Primary bubble 120 is cooled and collapsed as it passes through rollers 124.
  • the resulting collapsed tube is then re-inflated to form the second bubble.
  • the second bubble can be heated to a draw temperature by means of external heaters 148, 146, 144, and 142.
  • the amount of inflation determines the degree of orientation in the transverse direction.
  • Machine direction orientation can be imparted by having speed of the exit rollers 134 greater than the inlet rollers 128.
  • the double-bubble process can result in a biaxially oriented film that can be simultaneously oriented in both the machine and transverse directions. This is in contrast to the tenter frame processing line where first machine direction orientation can be followed by transverse (tenter direction) orientation.
  • the nucleant can be dispersed in the resinous polymer of propylene by any suitable procedure normally used in the polymer art to effect thorough mixing of a powder with a polymer resin.
  • the nucleant can be powder blended with resin in powder or pellet form or the nucleant can be slurried in an inert medium and used to impregnate or coat the resin in powder or pellet form.
  • powder and pellets can be mixed at elevated temperatures by using, for example, a roll mill or multiple passes through an extruder.
  • An example procedure for mixing can be the blending of nucleant powder and base resin pellets or powder and melt compounding this blend in an extruder.
  • this type of procedure can be used to form a masterbatch of pelletized resin containing sufficient nucleant so that when a masterbatch is let down in ratios of from about 10/1 to about 200/1 (polymer to nucleant) and blended with the base resin, the desired level of nucleant can be obtained in the final product.
  • a Q-dye masterbatch is formed by first adding a sufficient amount of the quinacridone dye to the polypropylene resin to form a polypropylene resin containing 40% of the quinacridone dye.
  • 3% of this concentrate can then be extrusion compounded with an additional 97% of polypropylene to make a new concentrate that contains 1.2% of the quinacridone dye ("the 1.2% concentrate").
  • a third compounding step can then be performed where 3% of the 1.2% concentrate is blended with 97% of polypropylene to make a new concentrate that contained 0.036% of the quinacridone dye.
  • a multi-component blending system can be used to precisely feed the different raw materials in to the hopper of an extruder. These raw materials typically consist of a neat polypropylene resin, a masterbatch containing the beta nucleant, and "re-grind" from previous extrusion runs or edge trim that can be taken off of the extruded sheet. As generally used herein, "re-grind” refers to portions of a previously extruded sheet that are ground up an added to the raw material feed used to make new sheet.
  • the neat polypropylene resin and the regrind generally do not contain an alpha nucleating agent.
  • the extruder melts and homogenizes the different raw materials, and then pumps out the molten extrudate.
  • a gear pump and a static mixer are often included in the extrusion system in order to provide for a consistent, homogeneous, and accurate flow of the polymer melt.
  • a sheet die which can evenly distribute the polymer melt across the desired sheet width.
  • the extruded sheet in the form of molten polymer can be quenched, or cooled, to solidify the molten sheet by a suitable quenching means.
  • the quenching means can be capable of quenching the sheet at a rate equal to or greater than the sheet production rate, and the temperature encountered by the sheet in the quenching means can be in a range suitable to promote the development of beta-spherulites.
  • the temperature range of the sheet during solidification can be from about 80 °C to about 130 °C.
  • Suitable quenching means include a single quench roll and a multi-roll quench stack, such as a two- roll, a three-roll or a five-roll quench stack.
  • the heated roll(s) cool the sheet uniformly and control the sheet thickness.
  • An on-line thickness profiler is typically used to control the sheet thickness to tight tolerances.
  • a three-roll vertical quench stack can be used with the sheet nipped between the first and the second rolls with the beta-spherulite crystallinity starting at the second or middle roll and the sheet wrapping around the middle and third rolls.
  • the temperature of the middle roll can be at least about 80 0 C 5 in one aspect, in the range of from about 90 0 C to about 130 0 C, for optimum production of beta-spherulites.
  • the temperature of the third roll can be in the range of about 80 0 C to about 110 0 C. However, if a single layer sheet with a very small amount of beta-spherulites near the sheet surfaces and a larger amount of beta-spherulites near the center is desired, the third roll temperature can be less than about 80 0 C. In one aspect, the temperature of the first roll of the three-roll stack can range from about 50 0 C to about 150 0 C without adversely affecting the beta-form content of the sheet.
  • the quenching means can be positioned relatively close to the extruder die, the distance between the quenching means and the extruder die can be dependent on factors such as the temperature of the rolls, the sheet extrusion rate, the sheet thickness, and the roll speed. Typically, the distance between the extruder die lips and the gap between the first and second heated rolls can be less than about 10 cm.
  • the finished sheet can then be wound onto a large roll for transfer to the next step in the process .
  • the extruded sheet may be one layer or multi-layered.
  • a multi-layered sheet can contain two layers, three layers, or more than three layers.
  • multi-layer and single layer sheets can be melt formed by coextrusion and extrusion, respectively, by various known shaping methods such as the calender method, the extrusion method, and the casting method.
  • An example method is melt extrusion slit-die or T-die process.
  • Extruders used in such a melt-extrusion process can be single-screw or twin-screw extruders. Such machines are generally free of excessively large shearing stress and are capable of kneading and extruding at relatively low resin temperatures.
  • one extruder can be used to extrude a sheet of the beta- spherulite nucleated resin.
  • a second extruder can be used to extrude a layer of non- nucleated polymer resin, which is located on at least one side of the nucleated resin.
  • a non- nucleated polymer melt can be split between two slit-dies and a second layer of extruded non-nucleated polymer sheet will be in contact with the other side of the beta-nucleated polymer resin layer between a second set of nip rolls.
  • more than one extruder can be used to supply molten polymer to a coextrusion die. This allows two or more distinct polymer layers to be coextruded from a given slit-die.
  • the temperature at the die exit can be controlled, such as through the use of a die-lip heater, to be the same as or slightly higher than the resin melt temperature. By controlling the temperature in this manner, "freeze-off of the polymer at the die lip can be prevented.
  • a die free of mars and scratches on the surface can produce a sheet with smooth surfaces. 4. Perforating the Sheet
  • the extruded sheet in a further aspect, after the extruded sheet solidifies, it can be passed through a sheet flattening unit, a perforator, and various orientation stations.
  • the perforator produces a series of holes or depressions in the sheet. These holes or depressions can be, for example, circular, oval, square, or rectangular in shape.
  • the perforations can be, for example, regularly or equally spaced.
  • the area of the holes or depressions is less than about 50% of the plain view area of the starting material, for example, less than about 25%.
  • the area of the perforations can be from about 5% to about 50%, from about 5% to about 25%, from about 25% to about 50%, from about 10% to about 20%, from about 30% to about 40%, or from about 40% to about 50% of the plain view area of the starting material.
  • Figure 1 illustrates the final steps in the process for manufacturing a plastic net (reinforcement grid or web).
  • the sheet can be un-rolled (5) and passed through a punch press (10), where a series of equally spaced holes can be punched out (15). Different hole geometries and punch arrangements are possible, depending on the desired properties of the finished net product.
  • the sheet After the sheet is extruded it can be oriented in one or two directions. During the orientation process the sheet develops micropores which can cause it to take on an opaque or translucent appearance.
  • the final microporous films can be used in a variety of applications such as tape, labels, packaging film, or battery separators.
  • a sheet that is oriented in one direction is typically used to reinforce earthen structures in civil engineering applications.
  • a sheet that is oriented in two directions is typically used to reinforce road beds.
  • the sheet If the sheet is to be oriented in only one direction, it passes through a machine direction (MD) orientation device, and is wound up on a winding unit.
  • MD machine direction
  • the draw ratios in the machine direction can vary from about 2:1 to about 10:1, for example, from about 3 : 1 to about 8:1.
  • Hot air or heated rollers can be used to heat the sheet to the appropriate stretching temperature.
  • the sheet can be stretched in the MD and the transverse direction (TD).
  • the TD stretching step can occur before or after the MD orientation step. Typically, the sheet is not cooled down substantially between the first and second stretches.
  • the sheet can pass through an oven that can be heated using either forced air or radiant heaters.
  • the TD orientation machine typically contains a series of clips attached to movable rails which hold the sides of the sheet. These rails diverge as the sheet passes through the TD machine, and this divergence can cause the sheet to stretch in the transverse direction.
  • a common name for the TD orientation machine is a Tenter Frame.
  • the TD draw ratios can be in the range of from about 2:1 to about 10:1, for example, in the range of about 3:1 to about 8:1.
  • the overall area stretch ratio of a biaxially stretched sheet can be at least about 13:1.
  • Figure 9 illustrates the formation of a monoaxially and biaxally oriented sheet.
  • the sheet In the first orientation step, the sheet can be heated by passing over a series of heated rollers within a housing (20). The sheet can then be heated up to the point where it can be stretched. The stretching can be accomplished by rotating the last roller in the series at a higher speed.
  • the MD oriented sheet can contain microvoids that are produced when the beta crystal phase transforms into the alpha crystalline phase during the stretching process.
  • the MD oriented sheet is typically white/opaque in appearance.
  • the MD oriented sheet in the second orientation step, can enter into a heated tenter frame (40) where the sheet is stretched in the transverse direction, i.e. at right angles to the initial MD stretch.
  • the tenter can be heated with forced air, and there can be two rails containing a series of clips, which grip the edge of the sheet as it passes into the tenter. These rails begin to diverge (44) after the sheet enters the tenter, and can cause the sheet to be stretched in the transverse direction. After the biaxially oriented film exits the tenter it can be wound onto a roll for shipment.
  • Figure 1 illustrates the formation of a biaxally oriented sheet for geogrid applications.
  • the sheet can be heated by passing over a series of heated rollers within a housing (20). The sheet is then heated up to the point where it can be stretched. The stretching is accomplished by rotating the last roller in the series at a higher speed, so that the polymer is drawn from the junctions into the ribs.
  • the MD oriented sheet can contain oblong holes (25).
  • Figure 2 shows an enlarged view of the MD oriented sheet. During this orientation step, the polymer molecules in the drawn regions are aligned in the machine direction, which imparts a great deal of strength and stiffness to the final net.
  • the drawing characteristics of the sheet and the shape of the holes and ribs can be different that the characteristics and shape found in sheets that do not contain beta spherulites.
  • the radius of curvature (r) of the drawn holes is smaller at the top and bottom of each hole, and the ribs can have a more flared-out appearance where they join together at the top and bottom of each hole.
  • the MD oriented sheet enters into a heated tenter frame (stenter) (30) where the sheet is stretched in the transverse direction, i.e. at right angles to the initial MD stretch.
  • the stenter is heated with forced air, and there are two rails containing a series of clips, which grip the edge of the sheet as it passes into the stenter. These rails begin to diverge (35) after the sheet enters the stenter, causing the sheet to be stretched in the transverse direction.
  • the biaxially stretched net exits the stenter in the form of a net or grid (40). After the net exits the stenter it is wound onto a roll for shipment (45).
  • FIG. 3 shows an enlarged view of the biaxially stretched net.
  • the biaxial orientation of the net imparts a high degree of orientation and strength to all regions of the net.
  • the drawing characteristics of the sheet change, and the shape of the holes (50), the drawn strands (55), and the nodes (60) in the net are different.
  • the most obvious differences are the reduced thickness of the node regions (60), which are normally much thicker than the drawn ribs and contain primarily un-drawn material.
  • the width of the node junction region is also greater in the net made from the beta nucleated sheet, and this enhances certain properties of the final web.
  • the stretching temperature during the orientation step(s) can be below about 160 0 C, for example, below about 155 0 C.
  • a stretching temperature of at least about 80 0 C can be used, and for example, this stretching temperature can be at least about 90 0 C, for example, 110 0 C.
  • the temperatures used to stretch the sheet can have a strong influence on its physical characteristics, including the degree of micro voiding which occurs during the stretching process. Since the beta-crystalline phase can have a lower tensile yield stress than the alpha-crystalline phase, a sheet containing a high level of beta-spherulites can be stretched at lower temperatures without breaking or tearing, compared to that of a sheet containing only alpha-spherulites. d. Rate
  • the beta-nucleated sheet can also be run at higher line speeds and stretched at higher drawing rates relative to that of a non-beta-nucleated sheet. These higher drawing rates can also produce higher degrees of polymer orientation in the sheet, which can lead to improved strength and stiffness properties in the final film or web product. 6. Properties of Resulting Film or Geogrid
  • the beta crystals When a sheet containing beta-spherulites is deformed in the solid state, i.e., at a temperature below the melting point of the beta-crystals, the beta crystals can transform into alpha crystals without first melting and develop micro voids or pores. This microvoiding also can cause a non-pigmented beta nucleated sheet to become white and opaque since the microvoids scatter light. The microvoiding also results in a final stretched sheet that has a lower density than that of a stretched sheet containing only alpha-crystals.
  • the degree of microvoiding depends on the concentration of beta-crystals, as measured by the K- value of the sheet or the size of the beta melting peak observed in a DSC scan, and the stretching temperature. Generally, the lower the stretch temperature, the higher the level of microvoiding and the lower the density of the final oriented film or web. However, too low a stretching temperature can be undesirable, since such a low temperature can lead to breaking or tearing of the sheet.
  • a sheet that contains a beta-nucleant and a high level of beta-spherulites can have a higher level of rigidity and is stronger than a sheet that does not contain any beta-spherulites.
  • the first is the likelihood that the beta-to-alpha transformation of the beta-crystals during the stretching process will lead to a more crystalline and more uniformly oriented material.
  • the second factor is the different drawing characteristics of the perforated beta nucleated sheet that is the precursor to the oriented polymer sheet, net, or grid. In the case of a beta nucleated grid, for example, more polymeric material is drawn out of the node regions, which lie at the intersection of the machine direction and transverse direction oriented strands comprising the grid structure. This material becomes part of the strands that form this grid, making the strands thicker and wider than they would be in the absence of beta nucleation.
  • the third factor is associated with the micro voiding and density reduction of the beta-nucleated sheet. Since the extruded sheets had the same starting thickness, the lower final density of the beta- nucleated net or grid demonstrates that this net or grid is thicker than a net or grid made from a sheet that is devoid of beta-spherulites.
  • Figure 4 and Equation I illustrate how to calculate the deflection of a beam that is supported at each end and deflected in the middle:
  • Equation II the moment of inertia (I) is calculated with Equation II:
  • the deflection of the beam under a given load can vary inversely as the cube of the thickness of the beam.
  • the rigidity of the beam, or the web made from the oriented extruded sheet will vary inversely with the deflection, and therefore will be proportional to the cube of the thickness of the web.
  • this decrease is typically less than the increase in the rigidity of the web caused by an increase in its thickness.
  • a beta-nucleated web can be formed so that it matches the strength and stiffness of the non-beta-nucleated web by reducing the thickness of the extruded beta- nucleated sheet.
  • less raw material is typically needed to produce a beta spherulite- containing polypropylene web with the same size (area), strength, and stiffness as a web formed of polypropylene without beta spherulites, than the raw material needed to form the web of polypropylene without beta spherulites.
  • the achievable weight reduction can be at least about 5%, for example, in excess of about 10%, based upon the weight of non- nucleated sheet material.
  • the preferred weight reduction can at least about 15%, based on the weight of non-nucleated sheet material.
  • the presence of beta spherulites in the extruded sheet can facilitate the process of post-stretching the perforated sheet to produce a uniaxially or biaxially oriented mesh structure, and can also broaden the temperature range over which this stretching can be performed. During the stretching process, the beta spherulites undergo microvoiding, causing the final mesh to have a lower density than a polypropylene mesh without beta spherulites.
  • the perforated beta nucleated sheet can also exhibit different stretching characteristics during the orientation steps than sheets without beta spherulites, such that more resinous polymer is drawn out of the node junction region between the machine direction (MD) and transverse direction (TD) oriented strands. Thus a greater percentage of the web area has solid polymer structure. This altered stretching behavior results in an oriented web that has higher strength and torsional rigidity characteristics.
  • MD machine direction
  • TD transverse direction
  • the extruded sheet can be one layer or multi-layered.
  • a multi-layered sheet can contain two layers, three layers, or more than three layers.
  • the sheet is a one-layer geo-web (geogrid or reinforcement grid).
  • At least one of the layers can contain beta spherulites so that, in one aspect, either (1) the K parameter is in the range of from about 0.1 to about 0.95, for example, in the range of from about 0.2 to about 0.95 or from about 0.3 to about 0.95, or (2) a prominent melting peak for the beta crystal phase can be shown when a sample of the sheet is placed in a DSC and heated at a rate of about 10 0 C per minute, where, in one aspect, the heat of fusion of the beta crystal phase is at least about 5% of the heat of fusion of the alpha crystal phase.
  • the beta spherulites can undergo microvoiding, which can cause the final film to have a lower density than a polypropylene film without beta spherul
  • the high strength and modulus of the strands that form the mesh, the reduced density, and the greater percentage of solid polymer in the web allows for the production of lighter weight mesh structures which meet all of the physical property requirements for end- use applications, such as reinforcing grids (geogrids) to stabilize concrete and soil in civil engineering and landfill applications.
  • the lighter weight extruded beta nucleated sheet can also be stretched at higher line speeds, and this higher productivity also reduces the cost of the final product.
  • a mesh that contains the same strength and modulus as a polypropylene mesh without beta spherulites can be formed from less raw material and at a faster rate when beta spherulites are used.
  • geogrids can be made by using a flat sheet die capable of forming sheets in a particular thickness range.
  • the thickness of such grids can be, for example, from about 0.01 inches to about 0.50 inches.
  • the beta nucleated sheets can also be oriented at higher production rates leading to improved productivity and reduced manufacturing costs.
  • the beta-spherulite content of the sheet or geogrid can be defined qualitatively by optical microscopy or quantitatively by x-ray diffraction or thermal analysis.
  • Optical microscopy In the optical microscopy method, a thin section microtomed from the sheet can be examined in a polarizing microscope by using crossed polars.
  • the beta-spherulites can show up as much brighter than the alpha spherulites, due to the higher birefringence of the beta-spherulites.
  • the beta-spherulites can occupy at least about 20% of the field of view, for example, at least about 30% of the field of view.
  • K an empirical parameter known as "K" (herein referred to as the "K- value”) can be defined by the equation:
  • the K-value can vary from 0, for a sample with no beta 7 crystals, to 1.0 for a sample with all beta-crystals.
  • the beta-spherulite nucleating agent can be Q-dye, which can be present in the composition in an amount ranging from about 0.1 to about 50 ppm.
  • the resulting sheet has a K-value in the range of from about 0.2 to about 0.95, for example, in the range of from about 0.3 to about 0.85. This is also a suitable range of K-values when other beta nucleants are used. 3.
  • Thermal Analysis [117] Thermal analysis of the extruded sheet can be characterized by Differential
  • DSC Scanning Calorimetry
  • the magnitude of the ⁇ Hf-beta parameter can provide a measure of how much beta crystallinity is present in the sample at the start of the heat scan.
  • the second heat of fusion values are reported, and these values represent the properties of the material after having been melted and recrystallized in the DSC at a cool-down rate of 10 °C/minute.
  • the first heat thermal scans can provide information about the state of the material before the heat history of the processing step used to make the samples had been wiped out.
  • the first heat thermal scan can show a distinct melting peak for the beta crystal phase, and the heat of fusion of the beta crystal phase can be at least about 5% of the heat of fusion of the alpha crystal phase.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • the examples relate to the production of a beta nucleated concentrate and the use of this concentrate to produce an extruded sheet from which oriented film products or biaxially oriented net or grid products are made.
  • the following nonlimiting examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for.
  • the beta nucleant was a red quinacridone dye, known as Hostaperm Red E3B, herein referred to as "Q-dye" (CAS No. 1047-16-1). This dye was incorporated into a polypropylene homopolymer resin (PRO- FAX 6523, produced by Basell Polyolefms) using extrusion compounding. The polypropylene resin had a melt flow rate of 4.0 g/10 min. The concentration of the Q-dye was 0.0075% (75 ppm).
  • the final pellets of this polypropylene Q-dye concentrate had a red color.
  • a second beta nucleant concentrate was prepared that contained a Q-dye concentration of 0.045% (450 ppm), and these pellets were also red in color.
  • Neutral color versions of these two concentrates were also prepared by incorporating an additional amount of a non-nucleating green dye into the concentrate in sufficient quantity to neutralize the red color.
  • the non-nucleating green dye that was used was in the form of a pellet concentrate produced by the Milliken Chemical Company, with the tradename of Cleartint Green 9807.
  • the ratio of the Cleartint Green 9807 to that of the of the Q-dye in the neutral color beta nucleant concentrate was 100 parts of the Cleartint Green 9807 to 1 part of the Q-dye.
  • the neutral color 75 ppm Q-dye concentrate pellets were gray in color, while the neutral color 450 ppm Q-dye concentrate pellets were almost black in color. 1.
  • the last roll in this series was moving at a faster speed (approximately six times as fast) than that of the previous roll, and the sheet was stretched as it passed between the slow and fast rolls.
  • This monoaxial oriented film which was identified as film #1, had a final thickness of 0.124 mm.
  • This oriented final film had a white/opaque appearance due to the presence of micro voids that were generated during the stretching process, and this microvoiding resulted from the presence of beta crystals in the extruded sheet.
  • a portion of the extruded sheet that was trimmed from the edge of the sheet before it passed through the orientation section was characterized using wide angle x-ray diffraction (WAXD), and a "K" value of 0.87 was measured.
  • WAXD wide angle x-ray diffraction
  • a second film sample was made which contained 95.5 % of the Dow 7C06 resin, 2.5% of the 75 ppm Q-dye concentrate, and 2% of a yellow pigment masterbatch.
  • This film identified as film #2, was processed using the same conditions as that of film #1.
  • An edge trim sample of the extruded sheet from this resin blend had a "K" value of only 0.05. The low K value observed here was believed to be the result of the fact that the yellow pigment was a nucleating agent for the alpha crystalline form of polypropylene, and therefore suppressed the formation of beta crystals in the extruded sheet.
  • a third film sample was made which contained 95.5% of the Dow 7C06 resin, 2.5% of the 450 ppm Q-dye concentrate, and 2% of the yellow pigment masterbatch.
  • This film identified as film #3, was processed using the same conditions as that of film #1.
  • An edge trim sample of the extruded sheet from this resin blend had a "K" value of 0.34.
  • a fourth film sample was made which contained 97.5% of the Dow 7C06 resin and 2.5% of the 450 ppm Q-dye concentrate. This sheet was extruded under the same conditions as that used for the previous sheet samples, but the maximum stretching temperature of the sheet was 125 °C. This film was identified as film #6. An edge trim sample of the extruded sheet from this resin blend had a "K" value of 0.88. a. Results
  • the sheet After exiting the extrusion die the sheet was cooled by contacting it with a heated metal roll that was set at a temperature of about 88 °C. The sheet was then stretched by passing it over a series of heated rolls set at a maximum temperature of 107 °C. The sheet was drawn between the slow roll and the fast roll, and the final film thickness was about 75 microns.
  • the beta nucleated versions of these sheets were produced by blending pellets of the neutral color 75 ppm Q-dye masterbatch with the each of the base polypropylene resins. Sheet and film were also produced under the same processing conditions using 100% of the base polypropylene resin.
  • Sample #2 which is the beta nucleated version of the impact copolymer, has a much lower density and a much higher opacity than that of sample #1, which is the non- nucleated impact copolymer.
  • sample #3 which is the two beta nucleated versions of the homopolymer, samples #4 and #5.
  • Sample #5 which contained a higher concentration of the beta nucleant and had a higher K value, exhibited a lower density and higher opacity than that of the lower K value homopolymer, sample #4.
  • the beta nucleated impact copolymer film had a very uniform opaque/white appearance, without the need to incorporate fillers and pigments.
  • the data also shows the unexpected and superior result that beta nucleation has a much stronger influence on density reduction and opacity when it is used with impact copolymer polypropylene resins as compared to its use in homopolymer polypropylene resins.
  • the end- user has the freedom to choose the most appropriate polypropylene resin to use for a given application in terms of melt flow rate and copolymer content.
  • Sample 3-1 was made using 100% of the PRO-FAX ® 7823, which is a polypropylene homopolymer produced by Basell Polyolefins, with a melt flow rate of about 0.7 g/10 min.
  • a beta nucleant or carbon black concentrate was not included in Sample 3- 1.
  • the line speed and roll gap nip were set to produce a final sheet thickness of 4.5 mm.
  • the line speed was 3.25 meters/minute, and the final sheet width after the edges were trimmed off was 1.0 meter.
  • Sample 3-2 was made under the same processing conditions as Sample 3-1, except 2.68% of the Q-dye concentrate was introduced into the feed, resulting in a final sheet that contained about 12 ppm of the Q-dye. This sheet had a light pink color.
  • Sample 3-3 was made under the same processing conditions as Sample 3-1, except that 3% of a carbon black concentrate was introduced into the feed along with 2.68% of the Q-dye concentrate. This sheet had a uniform black appearance.
  • Sample 3-4 had the same resin composition as that of Sample 3-3, except that the line speed was increased to reduce the thickness of the final sheet to 4.15 mm.
  • Sample 3-5 had the same resin composition as that of Sample 3-4, except that the line speed was further increased to reduce the final sheet thickness to 3.84 mm. a. Results [139] The compositions of the five different extruded sheet samples and the DSC thermal analysis data for Samples 3-1, 3-2, and 3-3 are listed in Table 3.
  • the white/opaque appearance of the Sample 3-2 strands is due to the microvoiding that occurred when the beta spherulites in the sheet were stretched.
  • the elongated holes in the Sample 3-2 sheet were also more closely spaced than those in the Sample 3-1 sheet after the MD stretching, and the overall width of the Sample 3-2 sheet was only about 94 cm, compared to a width of 100 cm for the stretched Sample 3-1 sheet.
  • Samples 3-1 and 3-2 sheets is illustrated in Figure 8. The various dimensions are tabulated in Table 4.
  • the density value obtained on the strands in Sample 3-2 sheet was 0.871 g/cm3, while the density of the strands in Sample 1 sheet was 0.907 g/cm 3 . This represents a density reduction of about 4% for the oriented strands of the beta nucleated Sample 3-2.
  • the grid made from the Sample 3-2 sheet had a smaller open mesh area, a wider node region, strands with higher cross sectional areas, and thinner node regions than the grid made from Sample 3-1. Both biaxially oriented grids contain the same number of mesh openings per unit area of sheet, since they both contained the same arrangement of punched-out holes.
  • the smaller mesh area of Sample 3-2 means that a greater percentage of the total mesh contains solid, oriented polymer. This difference reflects the fact that more material was drawn out of the node region in the sheet from Sample 3-2, and this extra polymer increases the percentage of the mesh structure that contains solid polymer. Since the strands from the mesh made from Sample 3-2 sheet have a greater cross-sectional area than the strands from the Sample 3-1 mesh, the Sample 3-2 grid will require higher forces to break when placed under tension.
  • the greater area of the junction regions in the Sample 3-2 grid indicates that the node regions have greater torsional rigidity and are better able to resist the forces present when the grid is used to reinforce roadbeds or other earthen structures than a net structure that does not contain beta- spherulites.
  • Example 5 Comparison of the Properties of Final Net or Grid Materials formed using Samples 3-3, 3-4, 3-5, and 3-6
  • Samples 3-3 and 3-6 both had the same starting sheet thickness of 4.5 mm, and the presence of beta spherulites in Sample 3-3 had an effect on the sheet dimensions that was similar to the effect on the dimension of the Sample 3-2 sheet (see Table 4). Thus, the Sample 3-3 sheet had a smaller mesh area, larger strand cross sectional area, a wider node region, and a thinner node hump than the Sample 3-6 sheet. As the starting sheet thickness decreased for the beta nucleated sheet samples (Samples 3-3, 3-4, and 3-5), the open mesh area increased and the thickness of the strand and node regions decreased.
  • TD Tensile Strength The true resistance to elongation when a mesh is cut from the grid and tested perpendicular to the machine direction and subjected to a load measured via ASTM D6637, with the load being measured after the sample has been deformed by 2% elongation.
  • MD and TD Ultimate Tensile Strength The maximum load that the mesh sample is subjected to before breaking or yielding occurs in either the machine direction (MD) or perpendicular to the machine direction (TD) when the sample is measured using ASTM D6637.
  • Mass The weight per unit area of the final biaxially oriented grid product.
  • Torsional Aperture Stability The resistance to in-plane rotational movement measured by applying a 20 kg-cm moment to the central junction of a 9 inch by 9 inch specimen restrained at its perimeter (U.S. Army Corps of Engineers Methodology for measurement of Torsional Rigidity).
  • Table 6 lists the physical properties of the biaxial grid products made from Samples 3-3, 3-4, 3-5, and 3-6.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention décrit des concentrés qui comprennent une résine de polypropylène et un agent de nucléation bêta. L'invention décrit également des feuilles de polypropylène extrudées qui comprennent les compositions décrites. On y décrit également des films produits en étirant les feuilles de polypropylène extrudées décrites. L'invention décrit également un procédé pour fabriquer les compositions, les feuilles et les films décrits.
PCT/US2005/028981 2004-08-17 2005-08-16 Concentrés de nucléation bêta Ceased WO2006023442A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/919,539 US20050043447A1 (en) 2003-04-16 2004-08-17 Beta nucleation concentrate
US10/919,539 2004-08-17
US11/053,519 2005-02-08
US11/053,519 US20060177632A1 (en) 2005-02-08 2005-02-08 Beta-nucleation concentrates for film applications

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Cited By (12)

* Cited by examiner, † Cited by third party
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DE102006034252A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
DE102006044041A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
DE102006062249A1 (de) * 2006-12-22 2008-06-26 Tesa Ag Trägerfolie, Verwendungen derselben sowie Verfahren zum Fibrillieren von Trägerfolien
EP2083042A1 (fr) * 2008-01-21 2009-07-29 Borealis Technology OY Composition de polypropylène coloré ayant un contenu élevé de modification ß
US20130149488A1 (en) * 2011-12-13 2013-06-13 3M Innovative Properties Structured film containing beta-nucleating agent and method of making the same
WO2013090380A1 (fr) * 2011-12-13 2013-06-20 3M Innovative Properties Company Film structuré contenant un agent de nucléation bêta et son procédé de fabrication
US9278471B2 (en) 2011-12-13 2016-03-08 3M Innovative Properties Company Method of detecting a component of an article and method of preparing a component for detection
CN105431123A (zh) * 2013-06-13 2016-03-23 3M创新有限公司 包括微孔膜的带
EP3359745A1 (fr) 2015-10-09 2018-08-15 Tensar Corporation, LLC Géogrille réalisée à partir de polymère multicouche coextrudé
CN109108350A (zh) * 2017-06-23 2019-01-01 胡兆栋 一种改进型挤光刀
US10376420B2 (en) 2013-06-13 2019-08-13 3M Innovative Properties Company Personal hygiene article and container for the same
US10704172B2 (en) 2014-04-10 2020-07-07 3M Innovative Properties Company Fibers and articles including them

Citations (2)

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US4374798A (en) * 1978-10-16 1983-02-22 P.L.G. Research Production of plastic mesh structure
US5277520A (en) * 1991-12-06 1994-01-11 The Tensar Corporation Grid composite for backfill barriers and waste applications

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US4374798A (en) * 1978-10-16 1983-02-22 P.L.G. Research Production of plastic mesh structure
US5277520A (en) * 1991-12-06 1994-01-11 The Tensar Corporation Grid composite for backfill barriers and waste applications

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006034252A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
DE102006044041A1 (de) * 2006-07-21 2008-01-24 Tesa Ag Monoaxial verstreckte Polypropylenfolie mit hohem Weiterreißwiderstand in Querrichtung
EP1881044A3 (fr) * 2006-07-21 2010-10-06 Tesa Se Feuille de polypropylène étiré monoaxialement dotée d'une haute résistance au déchirement dans le sens transversal
DE102006062249A1 (de) * 2006-12-22 2008-06-26 Tesa Ag Trägerfolie, Verwendungen derselben sowie Verfahren zum Fibrillieren von Trägerfolien
EP2083042A1 (fr) * 2008-01-21 2009-07-29 Borealis Technology OY Composition de polypropylène coloré ayant un contenu élevé de modification ß
WO2009092700A1 (fr) * 2008-01-21 2009-07-30 Borealis Technology Oy Composition de polypropylène coloré ayant une teneur élevée de modification ss
RU2450034C1 (ru) * 2008-01-21 2012-05-10 Бореалис Текнолоджи Ой ОКРАШЕННАЯ ПОЛИПРОПИЛЕНОВАЯ КОМПОЗИЦИЯ, ХАРАКТЕРИЗУЮЩАЯСЯ ВЫСОКИМ УРОВНЕМ СОДЕРЖАНИЯ β-МОДИФИКАЦИИ
US8383707B2 (en) 2008-01-21 2013-02-26 Borealis Technology Oy Coloured polypropylene composition having a high content of β-modification
CN101910220B (zh) * 2008-01-21 2013-04-17 博里利斯技术有限公司 具有高含量β-变体的有色聚丙烯组合物
JP2015510104A (ja) * 2011-12-13 2015-04-02 スリーエム イノベイティブ プロパティズ カンパニー 物品の構成要素を検出する方法及び検出のための構成要素を調製する方法
US10076450B2 (en) 2011-12-13 2018-09-18 3M Innovative Properties Company Structured film containing beta-nucleating agent and method of making the same
CN103987518A (zh) * 2011-12-13 2014-08-13 3M创新有限公司 含β-成核剂的结构化膜及其制备方法
US20130149488A1 (en) * 2011-12-13 2013-06-13 3M Innovative Properties Structured film containing beta-nucleating agent and method of making the same
US9278471B2 (en) 2011-12-13 2016-03-08 3M Innovative Properties Company Method of detecting a component of an article and method of preparing a component for detection
WO2013090380A1 (fr) * 2011-12-13 2013-06-20 3M Innovative Properties Company Film structuré contenant un agent de nucléation bêta et son procédé de fabrication
US9358714B2 (en) 2011-12-13 2016-06-07 3M Innovative Properties Company Structured film containing beta-nucleating agent and method of making the same
CN103987518B (zh) * 2011-12-13 2016-10-12 3M创新有限公司 含β-成核剂的结构化膜及其制备方法
EP3885129A1 (fr) * 2011-12-13 2021-09-29 3M Innovative Properties Co. Film structuré contenant un agent de nucléation bêta et son procédé de fabrication
CN105431123A (zh) * 2013-06-13 2016-03-23 3M创新有限公司 包括微孔膜的带
US10376420B2 (en) 2013-06-13 2019-08-13 3M Innovative Properties Company Personal hygiene article and container for the same
US10709619B2 (en) 2013-06-13 2020-07-14 3M Innovative Properties Company Fastening tape and mechanical fastener including microporous film
US10704172B2 (en) 2014-04-10 2020-07-07 3M Innovative Properties Company Fibers and articles including them
EP3359745A4 (fr) * 2015-10-09 2019-04-24 Tensar Corporation, LLC Géogrille réalisée à partir de polymère multicouche coextrudé
EP3359745A1 (fr) 2015-10-09 2018-08-15 Tensar Corporation, LLC Géogrille réalisée à partir de polymère multicouche coextrudé
US11198986B2 (en) 2015-10-09 2021-12-14 Tensar Corporation Method of making an integral geogrid from a coextruded multilayered polymer starting material
US11933013B2 (en) 2015-10-09 2024-03-19 Tensar Corporation, Llc Method of making an integral geogrid from a coextruded multilayered polymer starting material
CN109108350A (zh) * 2017-06-23 2019-01-01 胡兆栋 一种改进型挤光刀

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