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WO2015116382A1 - Compositions de polyéthylène expansé - Google Patents

Compositions de polyéthylène expansé Download PDF

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Publication number
WO2015116382A1
WO2015116382A1 PCT/US2015/011324 US2015011324W WO2015116382A1 WO 2015116382 A1 WO2015116382 A1 WO 2015116382A1 US 2015011324 W US2015011324 W US 2015011324W WO 2015116382 A1 WO2015116382 A1 WO 2015116382A1
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article
range
diene terpolymer
linear polyethylene
foamed
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Inventor
Pradeep P. Shirodkar
Jianya Cheng
Joseph M. TOMEI
Peijun Jiang
Arturo Leyva
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the present invention relates to diene terpolymers, and polyethylene compositions useful in foamable or foamed articles comprising linear polyethylenes and diene terpolymers.
  • Foamed sheets, films and other "articles” are used in many applications, particularly in blown-film applications including consumer trash bags, grocery bags, produce bags, pallet wrap, food wrap, liners, heavy duty bags, industrial bags, consumer bags, shrink films, labels, pouches for FFS packaging, tapes, stand-up pouches, lamination films, protective films, health and hygiene film applications. Similar thin foamed films can be made using cast film and sheet extrusion lines, but these will exhibit preferential orientation in the MD direction and hence weaker properties. Foamed films can be made in the form of monolayer or coextruded films with multiple layers, where one or more of the layers are foamed.
  • These thin foamed films can be further laminated to other substrates including, foil, paper, other plastics, or they can be post stretched in one or two directions for obtaining wrinkled skin surface effects.
  • substrates including, foil, paper, other plastics, or they can be post stretched in one or two directions for obtaining wrinkled skin surface effects.
  • polyolefin industry there has been a general trend to produce new high strength polymer resins. These resins have allowed film producers to down-gauge their product without sacrificing film strength or toughness.
  • High pressure LDPE resins have been used in foaming applications due to their relatively high melt strength, strain hardening behavior and easy processing.
  • MD machine direction
  • crosslinking is also being investigated as a way to improve mechanical support of thin foamed films. Crosslinking adds cost and complexity to the process, and results in material which cannot be easily recycled, and is therefore a less than ideal solution.
  • LLDPEs alone are known to have poor melt strength and this property is further reduced as the Melt index of the polymer is increased (that is, the molecular weight is reduced). For this reason, the use of these resins in non-cross linked foaming applications has been limited to blends in small amounts where the major component is a high melt strength polymer like Low Density Polyethylene, (LDPE).
  • LDPE Low Density Polyethylene
  • Publications of interest include: US 8,512,837; US 7,687,580; US 6,509,431 ; US 6,355,757; US 6,391,998; US 6,417,281; US 6,300,451 US 6,1 14,457; US 6,734,265; US 6,147, 180; US 6,870,010; US 5,670,595; US 4,657,81 1; US 4,533,578; WO 2013/043796; WO 2007/067307; WO 2002/085954; US 2007/0260016; US 2010/092709, US 2013/0090433; US 2013/209774; US 2013/224463; 2013/216812; Guzman, et al. in 56(5) AIChE Journal, 1325-1333 (2010); and "Bimodal polyethylene products from UNIPOLTM single gas phase reactor using engineered catalysts," Liu et al. in 195 MACROMOLECULAR SYMPOSIA, (2003).
  • the present invention is directed to a foamed or foamable article comprising (or consisting essentially of) a blend of a diene terpolymer and a linear polyethylene, the diene terpolymer comprising (or consisting essentially of) from 0.01 wt% to 10.0 wt% diene derived units, and 1.0 wt% to 20 wt% of C 4 to Cio a-olefin derived units based on the weight of the diene terpolymer, wherein the diene terpolymer: a) has a g' v i s of less than 0.90; b) has an Mw within a range of from 100,000 g/mol to 500,000 g/mol; c) has an Mw/Mn within the range of from 3.5 to 12.0, and d) an Mz/Mn of greater than 7.0.
  • Figure 1 is a graphical representation of GPC curves for a blend of 3 wt% of the branched modifier (or "diene terpolymer" (“DTP”) and EnableTM 3505 and neat Enable 3505 (comparative linear polyethylene having a g' v i s of greater than 0.90).
  • DTP branched modifier
  • EnableTM 3505 compound having a g' v i s of greater than 0.90
  • Figure 2 is a graphical representation of the Strain Hardening Behavior of the
  • Figure 3 is a graphical representation of the Melt Strength for inventive DTP
  • Figure 4 is a graphical representation of the Specific Gravity Reductions in the inventive blends.
  • Figure 5 are the micrographs of foam cell structures for foamed Enable 2010 and the corresponding 3% DTP blend.
  • This invention relates to a polyethylene-based, highly branched polyethylene diene terpolymer ("DTP") useful in blends with other polyolefins, especially other linear polyethylene polymers to form foamable or foamed articles.
  • DTP polyethylene-based, highly branched polyethylene diene terpolymer
  • the DTP improves the processability of linear polyethylenes when blended therewith, as can be evidenced, for example, by a decrease in the motor load of the extruder used to extrude the linear polyethylene.
  • the DTP can be described by a number of features and properties as measured.
  • the DTP also comprises from 0.01 or 0.05 or 1.0 wt% to 5.0 or 8.0 or 10.0 wt% diene derived units, preferably alpha- omega dienes, based on the weight of the DTP.
  • the dienes are most preferably selected from the group consisting of 1,4- pentadiene, 1,5-hexadiene, 1 ,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1 , 11 -dodecadiene, 1, 12-tridecadiene, 1,13-tetradecadiene, tetrahydroindene, norbornadiene also known as bicyclo-(2.2.1)-hepta-2,5-diene, dicyclopentadiene, 5-vinyl-2-norbornene, 1 ,4-cyclohexadiene, 1 ,5-cyclooctadiene, 1 ,7- cyclododecadiene, and combinations thereof.
  • the DTP preferably has a density within the range of from 0.890 or 0.905 or 0.910 or 0.915 g/cm 3 to 0.920 or
  • the properties of the DTP can of course vary depending on the exact process used to make it, but preferably the DTP has the following measurable features.
  • Certain DSC measurable properties include the following:
  • the DTP preferably has a melting point temperature (T m ) within the range of from 95 or 100 or 1 10 or 1 15°C to 125 or 130 or 135°C.
  • the DTP also preferably has a crystallization temperature (T c ) within the range of from 75 or 80 or 85 or 90°C to 1 10 or 1 15 or 120 or 125°C.
  • the DTP also preferably has a heat of fusion (Hf) within the range of from 70 or 75 or 80 J/g to 90 or 95 or 100 or 1 10 or 120 or 130 or 140 J/g.
  • the DTP preferably has a melt index ( 190°C/2 1 .6 kg, "I 2 ") of less than 5 or 4 or 3 or 2 or 1 or 0.5 g/10 min.
  • the DTP has a wide ranging high load melt index (I 21 ), but preferably has a high load melt index ( 190/21 .6, "I 21 ") of less than 10 or 8 or 6 or 4 or 2 or 1 g/10 min; or within the range of from 0. 15 or 0.50 or 0.80 or 1.0 g/10 min to 1 .5 or 4 or 5 or 6 or 8 or 10 g/10 min.
  • the DTP has a melt index ratio (MIR, or i/h) within a range of from 20 or 25 or 30 to 70 or 75 or 80 or 85 or 90.
  • the DTP preferably has a Complex Viscosity at 0. 1 rad/sec and a temperature of 190°C within the range of from 20,000, or 50,000, or 100,000 or 150,000 Pa » s to 300,000 or 350,000 or 400,000 or 450,000 Pa » s.
  • the DTP preferably has a Complex Viscosity at 100 rad/sec and a temperature of 190°C within the range of from 500 or 700 Pa » s to 5,000 or 8,000 or 10,000 or 15,000 Pa » s.
  • the DTP preferably has a Phase Angle at the Complex Modulus of 10,000 Pa within the range of from 10 or 15 or 20 or 25° to 45 or 50 or 55 or 60° when the complex shear rheology is measured at a temperature of 190°C.
  • the DTP preferably has a Phase Angle at the Complex Modulus of 100,000 Pa within the range of from 10 or 15° to 25 or 35 or 45° when the complex shear rheology is measured at a temperature of 190°C.
  • the DTP has a level of branching indicated by the measured value of the branching index "g'vis".
  • the value for g' v i s is preferably less than 0.95 or 0.92 or 0.90 or 0.80 or 0.75 or 0.60, or within a range of from 0.30 or 0.40 or 0.60 or 0.70 to 0.80 or 0.90 or 0.95.
  • a polyethylene is "linear" when the polyethylene has no long chain branches, typically having a g' v i s of 0.97 or above, preferably 0.98 or above.
  • Linear polyethylenes preferably include ethylene polymers having a g' v i s of 0.95 or 0.97 or more, and as further described herein. Thus, a lower value for g' v i s indicates more branching.
  • the inventive blends can however include blends of so-called long-chain branched LLDPEs with the DTP.
  • Shear thinning is observed for the DTPs and is a characteristic used to describe the diene terpolymer. "Shear thinning" is characterized by the decrease of the complex viscosity with increasing shear rate. One way to quantify the shear thinning is to use a ratio of complex viscosity at a frequency of 0.1 rad/s to the complex viscosity at a frequency of 100 rad/s. The "shear thinning ratio" is preferably greater than 10 or 20 or 30 or 40 or 50 for the DTPs used herein. More particularly, the shear thinning ratio of the DTP is within the range of from 5 or 10 or 20 to 40 or 50 or 60 or 70 or 100 or 200 or 300.
  • GPC GPC
  • the weight average molecular weight of the DTP, Mw, as measured by LS is within a range of from 100,000 or 120,000 or 150,000 or 250,000 g/mol to 300,000 or 350,000 or 400,000 or 500,000 g/mol; and the z-average molecular weight, Mz, as measured by LS, is preferably greater than 600,000 or 800,000 or 1,000,000 or 1,500,000 g/mole, or most preferably within a range of from 500,000 or 600,000 or 800,000 or 1,000,000 g/mol to 1,250,000 or 1,500,000 or 2,000,000 or 2,500,000 or 3,000,000 g/mole; and a number average molecular weight, Mn, as measured by DRI, is within a range of from 10,000 or 20,000 g/mol to 25,000 or 30,000 or 40,000 or 50,000 or 100,000 g/mole.
  • the Mw/Mn of the DTPs is preferably greater than 3.0 or 4.0 or 4.5 or 5.0 or 5.5 or 6.0 or 7.0, and is most preferably within a range of from 3.5 or 4.0 or 5.0 to 10 or 12; and the Mz/Mn is preferably greater than 7.0 or 10.0 or 15.0 or 20.0, or more, and most preferably within a range of from 7.0 or 10.0 or 15.0 or 20.0 to 30.0 or 35.0 or 40.0 or 50.0.
  • DRI differential reflection index
  • LS light scattering
  • the DTP can be made by techniques generally known in the art for making polyethylenes, preferably as described in US 2013/0090433, especially solution, gas phase, or slurry phase polymerization processes using single-site catalysis.
  • bridged tetrahydroindenyl zirconocenes or hafnocenes or substituted versions thereof are preferred single site catalysts when combined with known activator compounds such as perfluorinated organoboron compounds and/or aluminoxanes, most preferably methalumoxanes.
  • activator compounds such as perfluorinated organoboron compounds and/or aluminoxanes, most preferably methalumoxanes.
  • the catalyst composition is a bridged- bis(tetrahydroindenyl) zirconium dihalide or dialkyl, or bridged-bis(indenyl) zirconium dihalide or dialkyl, or substituted versions thereof, whereby the indenyl or tetrahydroindenyl chain may have Ci to C 10 alkyl or phenyl substitutions at any one or more positions, especially the 2, 4 or 7 positions relative to the bridging position.
  • the metallocenes are desirably activated with a so-called non-coordinating anion, preferably ⁇ , ⁇ -dialkyl anilinium tetrakis (perfluorinated aryl) borate, most preferably ⁇ , ⁇ -dimethyl anilinium tetrakis (heptafluoro-2-naphthyl) borate.
  • a so-called non-coordinating anion preferably ⁇ , ⁇ -dialkyl anilinium tetrakis (perfluorinated aryl) borate, most preferably ⁇ , ⁇ -dimethyl anilinium tetrakis (heptafluoro-2-naphthyl) borate.
  • Desirable temperatures at which to carry out the slurry phase process to make the DTP is within the range of from 50 or 60°C to 80 or 90 or 100 or 1 10°C. Hydrogen may be present in the slurry or solution process at a concentration of at least 50 ppm, or at least 100 ppm, or at least 150 ppm. Desirable temperature at which to carry out the solution phase processes to make the DTP is within the range of from 90 or 1 10°C to 130 or 140 or 160 or 180°C.
  • desirable C 4 to C 10 a-olefin comonomer concentrations in the reactor are within the range of from 0.1 or 0.5 or 1 wt% to 2 or 5 or 10 or 15 wt%, and desirable diene feed rates are within the range of from 0.01 or 0.05 or 0.1 wt% relative to ethylene feed rate to 0.1 or 0.2 or 0.5 wt%.
  • the DTPs are particularly useful as modifiers of "linear polyethylenes" such as LLDPEs or long chain branched polyethylenes (“LLDPE”) that are used to form films and other articles.
  • linear polyethylenes such as LLDPEs or long chain branched polyethylenes (“LLDPE”)
  • LLDPE long chain branched polyethylenes
  • highly branched LDPE is absent from the inventive blends.
  • linear polyethylenes include those such as disclosed in US 8,399,581 and US 7,951,873, and other traditional LLDPEs or so-called long-chain branched LLDPEs known in the art.
  • the DTP improves the melt strength of the linear polyethylenes as well as its processability (e.g., as evidenced by increased output relative to LLDPE alone) and its Dart Impact and Tear Strength when made into films and other articles.
  • compositions comprise, or preferably consist essentially of, or most preferably consist of a blend of LLDPE and the DTP.
  • Consist(ing) essentially of what is meant is that the blend may also include common additives such as antioxidants, anti-slip agents, colorants and pigments, and other common additives to a level no greater than 5 wt% or 4 wt% or 3 wt% or 2 wt%.
  • additives such as block, antiblock, antioxidants, pigments, fillers, processing aids, UV stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents may also be present.
  • Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium stearate, carbon black, low molecular weight resins and glass beads.
  • these additives are present, if at all, from 0.1 or 1.0 ppm to 500 or 1000 ppm.
  • the "linear polyethylene" useful in the foamable or foamed articles described herein have certain desirable features.
  • the linear polyethylene consists of ethylene derived units, and in other embodiments the linear polyethylene may comprise within a range of from 0.10 or 0.50 or 1.0 wt% to 2.0 or 3.0 or 5.0 or 10.0 wt% C 4 to C 12 a-olefin derived units, the remainder being ethylene derived units.
  • the linear polyethylene has a density within a range of from 0.915 or 0.920 or 0.925 g/cm 3 to 0.945 or 0.950 g/cm 3 .
  • the Haze value for such blends, or formed from such blends is preferably less than 50 or 40 or 30 or 20 or 10%.
  • the linear polyethylenes have certain desirable rheological properties.
  • the linear polyethylenes have an h (190°C/2.16 kg) within a range of from 0.50 or 0.80 g/10 min to 1.20 or 1.40 or 1.80 or 2.0 or 3.0 g/10 min.
  • the linear polyethylenes preferably have an I21 (190°C/21.6 kg) within a range of from 10 or 15 or 20 or 25 or 30 g/10 min to 40 or 45 or 50 g/10 min.
  • the I21/I2 of the linear polyethylene is within a range of from 10 or 20 or 25 to 35 or 40 or 50 or 60.
  • the linear polyethylenes useful in the articles also have certain desirable melt and crystalline properties.
  • the linear polyethylene has a melting point temperature (T m ) within a range of from 106 or 1 10 or 112°C to 134 or 138 or 140 or 144 or 148°C.
  • T m melting point temperature
  • T c crystallization temperature
  • the DTPs are preferably present as a blend with the "linear polyethylenes" to form the articles within a range of from 0.1 or 0.2 or 0.5 or 1.0 to 4 or 6 or 8 wt% by weight of the blend.
  • the blend is thus still considered unimodal in its GPC profile, but typically with a high molecular weight "bump” or "tail” as demonstrated in Figure 1.
  • this high molecular weight region is that of the DTP and is highly branched.
  • the linear polyethylene/DTP blend has a melt strength that is at least 5% higher than the melt strength of linear polyethylene used in the blend, preferably at least 10%, more preferably at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 100%, or at least 200%, or at least 300%, or at least 400%.
  • the melt strength of the DTP is within the range of from 5 or 10 or 15 or 20 or 30 cN to 40 or 50 or 60 cN, while that of the inventive blends is within the range of from 1 or 2 or 3 cN to 5 or 8 or 12 cN.
  • the polyethylene blends comprising one or more linear polyethylene and one or more DTPs show characteristics of strain-hardening in extensional viscosity.
  • Stress- hardening is observed as a sudden, abrupt upswing of the extensional viscosity in the transient extensional viscosity vs. time plot. This abrupt upswing, away from the behavior of a linear viscoelastic material, was reported in the 1960s for LDPE (J. Meissner, 8 RHEOLOGY ACTA., 78 (1969)) and was attributed to the presence of long branches in the polymer.
  • the inventive diene terpolymers and polyethylene blends have strain-hardening in extensional viscosity.
  • the "strain-hardening ratio" which is defined as the ratio of the maximum transient extensional viscosity over three times the value of the transient zero- shear-rate viscosity at the same strain rate, for the inventive blends is preferably within the range of from 0.5 or 2.0 or 3.0 to 6.0 or 7.0 or 8.0 or 9.0 or 10.0 when the extensional viscosity is measured at a strain rate of 1 sec-1 and at a temperature of 150°C.
  • the SHR can vary greatly, but is preferably within the range of from 4.0 or 5.0 or 10 to 20 or 40 or 60 at a strain rate of 1 sec-1 and at a temperature of 150°C.
  • the SHR of the blend is at least 10% higher than the SHR of the linear polyethylene used in the blend, preferably at least 20% higher, at least 30% higher, at least 50% higher, at least 100% higher, at least 500% higher, at least 800% higher, at least 1000% higher.
  • the inventive blend of the DTP with a linear polyethylene can improve the processability of the linear polyethylene.
  • Evidence of this is demonstrated, for example, in the improved ability to extrude the blend as compared to the linear polyethylene alone.
  • the average motor load of an extruder, in extruding the blend through a die has an average motor load of at least 1% or 2% or 3% or 4% or 5% or 8% or 10% less than the average motor load in the same extruder when extruding only the same linear polyethylene (or within a range of from 1 or 2 or 3% to 5 or 6 or 10%).
  • the output from the extruder may increase as much as 10 or 20 or 30 or 40% or more for the inventive blends relative to the linear polyethylene alone.
  • the DTP blend with linear polyethylene also preferably has a crystallization temperature (T c ) within the range of from 85 or 90 or 95°C to 1 10 or 115 or 120 or 125°C; or, more preferably, the T c of the blend is at least 4 or 6 or 8 or 10°C or more higher than that of the DTP alone.
  • T c crystallization temperature
  • the foamable and foamed articles of this invention typically utilize a foaming agent to cause expansion of the polymers by foaming.
  • the process of foaming is well known in the art, and any suitable means is useful in the present invention.
  • the inventive articles comprise (or consist essentially of) blends of the DTP and linear polyethylene and is thus “foamable”.
  • the blend preferably comprises (or consists essentially of) the DTP, linear polyethylene, and one or more foaming agents, in which case it is also "foamable.”
  • the article is said to be "foamed".
  • Particularly preferred foaming agents include both physical foaming agents and chemical foaming agents.
  • Chemical foaming agents include azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzene sulfonylsemicarbazide, p- toluene sulfonyl semi-carbazide, barium azodicarboxylate, N,N'-dimethyl-N,N'- dinitrosoterephthalamide, and trihydrazino triazine.
  • Some are known by their tradenames, such as HydrocerolTM by Boehringer Ingelheim Chemical Inc. (a sodium salt of polycarbonate acid and carbonate compounds in polyolefin matrix). As is known, this has a relatively low initiation temperature and the foaming agent can be selected to have a higher or lower initiation temperature as desired for a given application.
  • Chemical foaming agents also include organic foaming agents including aliphatic hydrocarbons having 1-9 carbon atoms, halogenated aliphatic hydrocarbons, having 1-4 carbon atoms, and aliphatic alcohols having 1-3 carbon atoms.
  • Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, and the like.
  • Chemical foaming agents include halogenated hydrocarbons, preferably fluorinated hydrocarbons.
  • fluorinated hydrocarbon examples include methyl fluoride; perfluoromethane; ethyl fluoride; 1 , 1 -difluoroethane (HFC- 152a); 1,1, 1-trifluoroethane (HFC- 143 a); 1, 1,1,2-tetrafluoro-ethane (HFC- 134a); pentafluoroethane; perfluoroethane; 2,2- difluoropropane; 1, 1, 1-trifluoropropane; perfluoropropane; perfluorobutane; and perfluorocyclobutane.
  • Partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include methyl chloride; methylene chloride; ethyl chloride; 1, 1,1- trichloroethane; 1, 1-dichloro-l-fluoroethane (HCFC-141b); 1-chloro- 1, 1 -difluoroethane (HCFC-142b); l, l-dichloro-2,2,2-trifluoroethane (HCFC-123); and 1-chloro- 1,2,2,2- tetrafluoroethane (HCFC-124).
  • Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12); trichlorotrifluoroethane (CFC-1 13); dichlorotetrafluoroethane (CFC-1 14); chloroheptafluoropropane; and dichlorohexafluoropropane. Fully halogenated chlorofluorocarbons are not preferred.
  • Aliphatic alcohols useful as foaming agents include methanol, ethanol, n-propanol, and isopropanol.
  • Suitable inorganic foaming agents useful in making the foams of the present invention include carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium.
  • Inorganic foaming agents also include sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; ammonium nitrite; nitroso compounds, such as N,N'-dimethyl-N,N'- dinitrosoterephthalamide and ⁇ , ⁇ '-dinitrosopentamethylene tetramine; azo compounds, such as azodicarbonamide, azobisisobutylonitrile, azocyclohexylnitrile, azodiaminobenzene, and bariumazodicarboxylate; sulfonyl hydrazide compounds, such as benzene sulfonyl hydrazide, toluene sulfonyl hydrazide, p,p'-oxybis(benzene sulfony
  • the amount of foaming agent incorporated into the polymer composition (typically the polymer melt) to make a foam-forming polymer composition (typically a gel) is preferably from 0.01 to 10 wt% and most preferably from 0.1 to 5 wt%, based on the total material in the blend.
  • the level of foaming agent is often altered to obtain a desired foam density.
  • a foaming assistant can be used with the foaming agent.
  • the simultaneous use of the foaming agent with a foaming assistant contributes to lowering of the decomposition temperature of the foaming agent, acceleration of decomposition and homogenization of bubbles.
  • the foaming assistant may include organic acids such as salicylic acid, phthalic acid, stearic acid and nitric acid, urea and derivatives thereof.
  • the amount of foaming assistant incorporated into the polymer composition (typically the polymer melt) is preferably from 0.01 to 10 wt% and most preferably from 0.1 to 5 wt%, preferably 0.5 to 3 wt%, based on the total material in the blend.
  • the foamed articles have certain desirable features.
  • the melt strength of the foamed article is within a range of from 2 or 4 cN to 8 or 10 cN.
  • the specific gravity of the foamed article is within a range of from 0.60 or 0.65 or 0.70 g/cm 3 to 0.80 or 0.85 or 0.90 g/cm 3 .
  • the specific gravity of the foamed article is reduced by at least 5 or 8 or 10 or 15 or 20% relative to the foamed linear polyethylene without the diene terpolymer.
  • compositions of this invention may be used in any known application involving molding or extrusion, including consumer goods, industrial goods, construction materials, packaging materials, and automotive parts.
  • the foam articles can be used as weather seals for the automotive industry, where the object is to reduce road noise, dust, grit, and moisture intake at the various openings, such as window seals, door seals, and trunk seals.
  • the elastomeric characteristics of the inventive composition allow it to conform to the shapes needed and to be effectively compressed into gaps and corners at the openings of the automotive openings when they are closed such that compressed foam hinders the entry of the noise, dust, and moisture.
  • polyethylene foam offers a lightweight packaging solution with excellent grease/fat/oil resistance. Its high heat stability means products are microwaveable, with good thermal insulation giving them a 'cool touch' during removal.
  • SEC-DRI-LS-VIS a viscometer
  • Three Polymer Laboratories PLgel 10mm Mixed-B columns are used.
  • the nominal flow rate is 0.5 cm 3 /min and the nominal injection volume is 300 ⁇ ⁇ .
  • the various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135°C.
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre- filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
  • TCB 1,2,4-trichlorobenzene
  • Two diene terpolymers (Examples 1 and 2) were produced for evaluation of the inventive foamable or foamed articles.
  • the two diene terpolymers were made in a continuous stirred-tank reactor operated in a solution process.
  • the reactor was a 1.0-liter stainless steel autoclave reactor and was equipped with a stirrer, a water cooling/steam heating element with a temperature controller and a pressure controller.
  • Solvents and all monomers were first purified by passing through a three-column purification system.
  • the purification system consisted of an Oxiclear column (Model No. RGP-R1-500 from Labclear) followed by a 5A and a 3A molecular sieve column.
  • the purified solvents and monomers were then chilled to about -15°C by passing through a chiller before being fed into the reactor through a manifold.
  • Ethylene was delivered as a gas solubilized in the chilled solvent/monomer mixture.
  • Solvent and monomers were mixed in the manifold and fed into the reactor through a single tube.
  • 1,9-decediene was diluted with isohexane and fed into the reactor using a metering pump. All liquid flow rates were measured using Brooksfield mass flow controller.
  • the catalyst used was rac-dimethylsilylbis(indenyl)zirconium dimethyl.
  • the metallocenes were pre-activated with an activator of ⁇ , ⁇ -dimethyl anilinium tetrakis (heptafluoro-2-naphthyl) borate at a molar ratio of about 1 : 1 in toluene.
  • the preactivated catalyst solution was kept in an inert atmosphere and was fed into the reactor by a metering pump through a separated line. Catalyst and monomer contacts took place in the reactor.
  • TNOA tri-n-octyl aluminum
  • the collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours.
  • the vacuum oven dried samples were weighed to obtain yields. All the reactions were carried out at a pressure of about 2 MPa.
  • the polymerization process condition and some characterization data are listed in Table 1. For each polymerization run, the catalyst feed rate and scavenger feed rate were adjusted to achieve a desired conversion listed in Table 1.
  • Experimental Ziegler-Natta PE is a 0.944D/1.25MI polyethylene produced by Ziegler Natta catalyst with no long chain branching.
  • the DTP was homogenized with an antioxidant package (500 ppm Irganox 1076 and 2,000 ppm Weston 399) in a 1" Haake twin screw extruder and was pelletized. 3% pelletized DTP was further mixed with the corresponding base resin in the same 1" Haake twin screw extruder to form the blends.
  • the extrusion conditions for both DTP homogenization and the blend compounding are the same and are listed in Table 3. Table 3.
  • the foaming experiments were conducted on a single extruder foaming line.
  • the extruder used was a 2.5" Davis, 30: 1 L/D, water cooled barrels.
  • the screw design was a GP with a Maddock mixing section.
  • the die design is an adjustable flex lip, 12" wide, internal coat hanger design with an "R" bar (restrictor bar) to manipulate flow.
  • the thickness range was 0.020" to about 0.1 10".
  • a set of 3 stack rolls of 36" wide and about 1 foot in diameter were used to cool, keep foamed sheet flat and improve the surface appearance. Typical process conditions are shown in Table 4 below.
  • Figure 5 is a micrograph showing the advantageous features of the foamed blend and article.
  • the micrograph on the left in Figure 5 corresponds to Example A, and the one on the right to Figure B.
  • These two micrographs illustrate the advantage of DTP addition.
  • the cell population is much higher in the DTP blend, which is directly related to the foamed article density reduction.
  • the cell size appears to be smaller and the cells are well distributed.
  • the cells are still all closed cells at higher population. Close cell is conducive for better mechanical properties.
  • a foamed or foamable article comprising (or consisting essentially of) a blend of a diene terpolymer and a linear polyethylene, the diene terpolymer comprising from 0.01 wt% to 10.0 wt% diene derived units, and 1.0 wt% to 20 wt% of C 4 to C 10 a- olefin derived units based on the weight of the diene terpolymer, wherein the diene terpolymer has:
  • the diene terpolymer comprises (or consists of) ethylene derived units and diene derived units, most preferably alpha-omega diene derived units; wherein the diene terpolymer also comprises within the range from 1.0 or 2.0 or 5.0 wt% to 12 or 16 or 20 wt% of a C 4 to C 10 a-olefin derived units based on the weight of the diene terpolymer.
  • the diene is selected from the group consisting of: 1 ,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1, 11-dodecadiene, 1,12- tridecadiene, 1, 13-tetradecadiene, tetrahydroindene, norbornadiene also known as bicyclo-(2.2.1)-hepta-2,5-diene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4- cyclohexadiene, 1,5-cyclooctadiene, 1,7-cyclododecadiene, and combinations thereof.
  • the DTP has a density within the range of from 0.890 or 0.905 or 0.9
  • PI 1 The article of any one of the previous paragraphs, wherein the linear polyethylene has a density within a range of from 0.915 or 0.920 or 0.925 g/cm 3 to 0.945 or 0.950 g/cm 3 .
  • PI 4 The article of any one of the previous paragraphs, wherein the I21/I2 of the linear polyethylene is within a range of from 10 or 20 or 25 to 35 or 40 or 50 or 60.
  • PI 6 The article of any one of the previous paragraphs, wherein the linear polyethylene has a crystallization temperature (Tc) within a range of from 95 or 100 °C to 1 15 or 120 or 125 or 130°C.
  • Tc crystallization temperature
  • PI 7 The article of any one of the previous paragraphs, wherein the diene terpolymer has a strain hardening ratio of 3 or more.
  • PI 8 The article of any one of the previous paragraphs, wherein the blend also comprises a foaming agent within the range of from 0.5 or 1.0 or 2.0 wt% to 3.0 or 4.0 or 5.0 or
  • melt strength of the foamed article is within a range of from 2 or 4 cN to 8 or 10 cN.
  • DTP in a blend with a linear polyethylene to form a foamable or foamed article.

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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)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un article pouvant être expansé ou expansé comprenant un terpolymère diène, le terpolymère diène comprenant (ou étant constitué essentiellement de) 0,01 % en poids à 10,0 % en poids de motifs dérivés de diène, et 1,0 % en poids à 20 % en poids de motifs dérivés d'a-oléfine en C4 à C10 par rapport au poids du terpolymère diène. Le terpolymère diène : a) a un g'vis inférieur à 0,90 ; b) a un Mw dans une plage de 100 000 g/mole à 500 000 g/mole ; c) a un Mw/Mn dans la plage de 3,5 à 12,0 ; et d) un Mz/Mn supérieur à 7,0. Les articles inventifs comprennent un mélange d'un polyéthylène linéaire relativement haute densité et du terpolymère diène.
PCT/US2015/011324 2014-01-30 2015-01-14 Compositions de polyéthylène expansé Ceased WO2015116382A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018182943A1 (fr) * 2017-03-29 2018-10-04 Exxonmobil Chemical Patents Inc. Compositions de polyéthylène
US10125247B2 (en) 2014-05-29 2018-11-13 Exxonmobil Chemical Patents Inc. Polyethylene compositions
US10562219B2 (en) 2014-05-29 2020-02-18 Exxonmobil Chemical Patents Inc. Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof
WO2021119158A1 (fr) * 2019-12-09 2021-06-17 Exxonmobil Chemical Patents Inc. Films de polyéthylène orientés biaxialement et leur procédé de production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053364A1 (fr) * 2000-01-18 2001-07-26 Mobil Oil Corporation Terpolymeres
WO2007136494A2 (fr) * 2006-05-17 2007-11-29 Dow Global Technologies Inc. PROCÉDÉ DE POLYMÉRISATION D'UNE SOLUTION D'ÉTHYLÈNE/ α-OLÉFINE/ DIÈNE ET POLYMÈRE CORRESPONDANT
US20080033112A1 (en) * 2006-08-04 2008-02-07 Squire Kevin R Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers
US20130090433A1 (en) * 2011-09-23 2013-04-11 Exxonmobile Chemical Patents Inc. Modified Polyethylene Compositions
US20130216812A1 (en) * 2011-09-23 2013-08-22 Exxonmobil Chemical Patents Inc. Modified Polyethylene Compositions with Enhanced Melt Strength

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053364A1 (fr) * 2000-01-18 2001-07-26 Mobil Oil Corporation Terpolymeres
US6509431B1 (en) * 2000-01-18 2003-01-21 Exxonmobil Oil Corporation Terpolymers
WO2007136494A2 (fr) * 2006-05-17 2007-11-29 Dow Global Technologies Inc. PROCÉDÉ DE POLYMÉRISATION D'UNE SOLUTION D'ÉTHYLÈNE/ α-OLÉFINE/ DIÈNE ET POLYMÈRE CORRESPONDANT
US20080033112A1 (en) * 2006-08-04 2008-02-07 Squire Kevin R Polymer compositions comprising cyclic olefin copolymers and polyolefin modifiers
US20130090433A1 (en) * 2011-09-23 2013-04-11 Exxonmobile Chemical Patents Inc. Modified Polyethylene Compositions
US20130216812A1 (en) * 2011-09-23 2013-08-22 Exxonmobil Chemical Patents Inc. Modified Polyethylene Compositions with Enhanced Melt Strength

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10125247B2 (en) 2014-05-29 2018-11-13 Exxonmobil Chemical Patents Inc. Polyethylene compositions
US10562219B2 (en) 2014-05-29 2020-02-18 Exxonmobil Chemical Patents Inc. Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof
WO2018182943A1 (fr) * 2017-03-29 2018-10-04 Exxonmobil Chemical Patents Inc. Compositions de polyéthylène
WO2021119158A1 (fr) * 2019-12-09 2021-06-17 Exxonmobil Chemical Patents Inc. Films de polyéthylène orientés biaxialement et leur procédé de production

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