ZA200006429B - Extrudable vinylidene chloride polymer compositions. - Google Patents
Extrudable vinylidene chloride polymer compositions. Download PDFInfo
- Publication number
- ZA200006429B ZA200006429B ZA200006429A ZA200006429A ZA200006429B ZA 200006429 B ZA200006429 B ZA 200006429B ZA 200006429 A ZA200006429 A ZA 200006429A ZA 200006429 A ZA200006429 A ZA 200006429A ZA 200006429 B ZA200006429 B ZA 200006429B
- Authority
- ZA
- South Africa
- Prior art keywords
- vinylidene chloride
- polymer
- composition
- glycerol ester
- layer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims description 92
- 239000000203 mixture Substances 0.000 title claims description 89
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims description 85
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 49
- -1 glycerol ester Chemical class 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 35
- 239000010410 layer Substances 0.000 claims description 34
- 229920000620 organic polymer Polymers 0.000 claims description 30
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 25
- 229920000098 polyolefin Polymers 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920001903 high density polyethylene Polymers 0.000 claims description 14
- 239000004700 high-density polyethylene Substances 0.000 claims description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 13
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 9
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 6
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- QHZLMUACJMDIAE-UHFFFAOYSA-N 1-monopalmitoylglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(O)CO QHZLMUACJMDIAE-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 235000019485 Safflower oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 235000005713 safflower oil Nutrition 0.000 claims description 2
- 239000003813 safflower oil Substances 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 150000005691 triesters Chemical class 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 239000001993 wax Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 206010040904 Skin odour abnormal Diseases 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- GGJRAQULURVTAJ-PDBXOOCHSA-N rac-1-alpha-linolenoylglycerol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OCC(O)CO GGJRAQULURVTAJ-PDBXOOCHSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/08—PVDC, i.e. polyvinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- 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)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Description
EXTRUDABLE VINYLIDENE CHLORIDE POLYMER COMPOSITIONS
This invention relates to vinylidene chloride polymer (PVDC) compositions having improved extrudability.
To control the generation of PVDC degradation products during meit- processing, processing aids such as lubricants (for example, internal and external types), olefinic waxes and oils have been blended with the vinylidene chloride polymer prior to fabrication into a final product. However, it has been found that, after prolonged periods of extrusion under desirable processing conditions, an excessive degree of adhesion develops between the vinylidene chloride polymer and the metal surfaces of the extruder screw and die. This adhesion increases the residence time of the vinylidene chloride polymer which promotes degradation, resulting in the formation of die face buildup or die slough generation, and in the generation of carbon buildup on the screw and die metal surfaces.
It would be desirable to provide a vinylidene chloride polymer composition which is capable of being extruded, in either powder or pellet form, without having an unacceptable level of degradation which results from excessive adhesion between the PVDC melt and the screw and die metal surfaces.
In a first aspect, the present invention is a vinylidene chloride polymer (PVDC) composition comprising (1) a vinylidene chloride polymer, (2) a glycerol ester and (3) a silicone polymer, the glycerol ester and silicone polymer being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer.
In a second aspect, the present invention is a vinylidene chloride polymer (PVDC) composition comprising (1) a vinylidene chloride polymer, (2) a glycerol ester, (3) a silicone polymer and (4) an epoxidized processing aid, the glycerol ester, silicone polymer and epoxidized processing aid being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer.
In a third aspect, the present invention is a vinylidene chloride polymer (PVDC) composition comprising (1) a vinylidene chloride polymer, (2) a glycerol ester and (3) a polyolefin, the glycerol ester, and polyolefin being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer.
The inventors have discovered that adding a glycerol ester and a silicone polymer or a polyolefin and, optionally, an epoxidized processing aid to PVDC improves the extrudability of the PVDC by reducing its degree of adhesion to the metal surfaces of the screw and die. The PVDC compositions of the present invention are considered to possess improved extrudability. As used herein, the term "improved extrudability" means that, if subjected to desirable processing conditions in an extruder, the polymer composition is less thermally sensitive and, consequently, the extrudate possesses a reduced level of degraded material in the form of die face buildup, slough generation and carbon buildup on extruder screw and die surfaces, reduced discoloration or less hydrogen chloride evolvement and a lower mechanical energy to extrude, that is, amount of energy expended to extrude the polymer due to friction and the viscosity of the polymeric composition, than a PVDC composition which does not contain the silicone/carrier polymer concentrate.
Vinylidene chloride polymers which can be employed in the practice of the present invention are well-known in the art. See, for example, U.S. Patents 3,642,743 and 3,879,359. The most common PVDC resins are known as Saran™ resins, manufactured by
The Dow Chemical Company. As used herein, the term "vinylidene chloride polymer” or "PVDC" encompasses homopolymers of vinylidene chloride, and also copolymers and terpolymers thereof, wherein the major component is vinylidene chloride and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer. Monoethylenically unsaturated monomers which can be employed in the practice of the present invention for preparing the vinylidene chloride polymers include vinyl chloride, alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, and methacrylonitrile. Preferred ethylenically unsaturated monomers include vinyl chloride, acrylonitrile, methacrylonitrile, alkyl acrylates, and alkyl methacrylates. More preferred ethylenically unsaturated monomers include vinyl chloride, acrylonitrile, methacrylonitrile, and the alkyl acrylates and alkyl methacrylates having from 1 to 8 carbon atoms per alkyi group. Most preferred ethylenically unsaturated monomers are vinyl chloride, methylacrylate, ethylacrylate, and methyl methacrylate.
Preferably, the vinylidene chloride polymer is formed from a monomer mixture comprising a vinylidene chloride monomer generally in the range of from 60 to 99 weight percent and the monoethylenically unsaturated comonomer in an amount of from 40 to 1 weight percent, said weight percents being based on total weight of the vinylidene chloride interpolymer. More preferably, the amount of monoethylenically unsaturated monomer is from 40 to 4 weight percent, and most preferably, from 40 to 6 weight percent, based on total weight of the vinylidene chloride polymer.
The glycerol esters which can be employed in the practice of the present invention for preparing the vinylidene chloride polymer composition are those having from 14 to 22 carbon atoms, such as, for example, glycerol monostearate, glycerol monopalmitate, glycerol monooleate, glycerol monolinooleate, glycerol monolinolenate and their corresponding di- and triesters. The preferred glycerol ester is glycerol monostearate.
The amount of glycerol ester which can be employed in the present invention depends on the composition of the vinylidene chloride polymer composition and the processing conditions to which the vinylidene chloride polymer composition is exposed, but in general, the amount is from 0.05 to 10, preferably from 0.2 to 5 and most preferably 2 weight percent, based on the weight of the vinylidene chloride polymer composition.
The silicone polymers which can be employed in the practice of the present invention for preparing the vinylidene chloride composition include the high viscosity silicone fluids. The term “high viscosity silicone fluids" as used herein is intended to represent a wide range of polysiloxane materials having a high molecular weight. These high viscosity silicone fluids, often characterized as silicone gums, are comprised of 20 to 100 percent siloxane polymers having an average molecular weight of 50,000 or above and provide a viscosity of 90,000 centipoise and above at ambient temperature. The preferred polysiloxanes are polydimethyl siloxane, polydimethyldiphenyl siloxane and polymethyl alkyl aryl siloxane. It is known that these fluids are difficult to handie and feed into conventional blending equipment with solid thermoplastic polymers due to their high viscosity. See, for example, U.S. Patent 4,446,090.
The high viscosity silicone fluids are employed in the practice of the present invention in the form of concentrates. The silicone polymer concentrate can be prepared by blending the high viscosity silicone polymer and a carrier polymer (for example HDPE) in the melt using conventional melt-processing techniques. Conventional melt-processing equipment which may be used includes heated two-roll compounding mills, Brabender mixers, Banbury mixers, single screw extruders, and twin screw extruders. It is desirable that the silicone polymer and carrier polymer be blended under conditions and for a time sufficient to produce a visually homogeneous blend of the silicone polymer and carrier polymer.
The amount of silicone polymer employed in the practice of the present invention for preparing the concentrate is from 0.1 to 99.9, preferably from 10 to 90 and, most preferably, from 25 to 75 weight percent, based on the weight of the concentrate.
The carrier polymers which can be employed in the practice of the present invention for preparing the concentrate are those which are known in the art for imparting beneficial properties to vinylidene chloride polymers, such as, for example, polyolefins, oxidized polyolefins, ethylene vinyl acetate copolymers, and acrylate copolymers.
Preferably, the carrier polymer is a polyolefin, more preferably, a polyethylene and, most preferably, a high density polyethylene (HDPE).
The amount of carrier polymer employed in the practice of the present invention for preparing the concentrate is from 0.1 to 99.9, preferably from 10 to 80 and, most preferably, from 25 to 75 weight percent, based on the weight of the concentrate.
The most preferred silicone/carrier polymer concentrate is commercially available from Dow Corning as a 50/50 weight percent blend of a high viscosity, high molecular weight polydimethyl siloxane and HDPE.
The silicone/carrier polymer concentrate of the present invention is typically blended with the vinylidene chloride polymer in an amount sufficient to provide from 0.01 to 10 weight percent silicone/carrier polymer concentrate in the blend.
Other types of silicone polymers which can be employed in the present invention include low viscosity silicone fluids, such as those having a viscosity of at least about 100 centipoise at 25°C.
The amount of silicone polymer present in the vinylidene chloride polymer composition of the present invention depends on the composition of the vinylidene chloride polymer composition and the processing conditions to which the vinylidene chloride polymer composition is exposed. In general, the amount of silicone polymer present in the vinylidene chloride polymer composition is from 0.005 to 5.0, preferably from 0.02 to 0.2 and most preferably 0.1 weight percent, based on the weight of the vinylidene chloride polymer composition.
The epoxidized processing aids which can be used in the practice of the present invention for preparing the vinylidene chloride polymer composition include the epoxidized vegetable oils, such as linseed oil, soybean oil, coconut oil, safflower oil, sunflower oil, and cotton seed oil; and the epoxidized fatty acid monoesters, such as, octyl stearate; and epoxidized diesters, such as the glycol ester of an unsaturated fatty acid, such as glycol dioleate.
The amount of epoxidized stabilizer which can be employed in the present invention depends on the composition of the vinylidene chloride polymer composition and the processing conditions to which the vinylidene chloride polymer composition is exposed, but in general, the amount is from 0.1 to 10, preferably from 0.4 to 4 and most preferably 1 weight percent, based on the weight of the vinylidene chloride polymer composition.
A variety of conventional additives may also be incorporated into the vinylidene chloride polymer composition. Additive type and amount will depend upon several factors. One factor is the intended use of the composition. A second factor is tolerance of the composition for the additives. That is, how much additive can be added before physical properties of the blends are adversely affected to an unacceptable level. Other factors are apparent to those expert in the art of polymer formulation and compounding.
Exemplary additives include plasticizers, heat stabilizers, pigments, processing aids, lubricants, fillers, and antioxidants. Each of these additives is known and several types of each are commercially available.
Exemplary lubricants include fatty acids, such as stearic acid; esters, such as fatty esters, wax esters, glycol esters, and fatty alcohol esters; fatty alcohols, such as n-stearyl alcohol; fatty amides, such as N,N'-ethylene bis stearamide; metallic salt of fatty acids, such as calcium stearate, zinc stearate, magnesium stearate; and polyolefin waxes, such as paraffinic, and oxidized polyethylene. Paraffin and polyethylene waxes and their properties and synthesis are described in 24 Kirk-Othmer Encyc. Chem. Tech. 3rd Ed.,
Waxes, at 473-77 (J. Wiley & Sons 1980).
The additives may be incorporated into the vinylidene chloride polymer composition by using conventional melt-processing, as well as dry blending techniques for thermally sensitive polymers. The vinylidene chloride polymer composition of the present invention can be melt-processed and extruded into any suitable final product, for example, a variety of films or other articles. As is well known in the art, the films and articles are fabricated with conventional coextrusion; for example, feedblock coextrusion, multimanifold die coextrusion, or combinations of the two; injection molding; co-injection molding; extrusion molding; casting; blowing; blow molding; calendering; and laminating.
Exemplary articles include blown and cast, mono and multilayer, films; rigid and flexible containers; rigid and foam sheet; tubes; pipes; rods; fibers; and various profiles.
Lamination techniques are particularly suited to produce multi-ply sheets. Asis known in the art, specific laminating techniques include fusion; that is, whereby self-sustaining lamina are bonded together by applications of heat and pressure; wet-combining, that is, whereby two or more plies are laminated using a tie-coat adhesive, which is applied wet, the liquid driven off, and in one continuous process combining the plies by subsequent pressure lamination: orby heat reactivation, that is, combining a precoated film with another film by heating, and reactivating the precoat adhesive so that it becomes receptive to bonding after subsequent pressure laminating.
The vinylidene chloride polymer compositions of the present invention are particularly suited for fabrication into flexible and rigid containers both in monolayer and multilayer structures used for the preservation of food, drink, medicine and other perishables. Such containers should have good mechanical properties, as well as low gas permeabilities too, for example, oxygen, carbon dioxide, water vapor, odor bodies or flavor bodies, hydrocarbons or agricultural chemicals.
The monolayer structures comprise the vinylidene chloride polymer composition of the present invention.
The multilayer structure comprises (1) one or more layers of an organic polymer or a blend of two or more different organic polymers, the organic polymer of one layer being the same as or different from the organic polymer of another layer and (2) one or more layers of the vinylidene chloride polymer composition of the present invention.
The multilayer structure can have three layers comprising (1) a first outer layer of the organic polymer or blend of two or more different organic polymers, (2) a core layer of the vinylidene chloride polymer composition of the present invention and (3) a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer.
The multilayer structure can also have five or seven layers comprising one or more layers of the vinylidene chloride polymer composition of the present invention, and the -6- i remaining layers comprising an organic polymer or a blend of two or more different organic polymers, the organic polymer of one layer being the same as or different from the organic polymer of another layer.
Adhesive layers may be interposed between contiguous layers of the multilayer structures, depending on the composition and method of preparing the multilayer structure.
Organic polymers which can be used in the practice of the present invention for preparing the multilayer structure include polyolefins, polyamides, polymers based on aromatic monomers, and chlorinated polyolefins.
By the term “polyolefin” is meant a polymer or copolymer of ethylene, that is, a polymer derived solely from ethylene, or ethylene and one or more monomers copolymerizable therewith. Such polymers (including raw materials, their proportions, polymerization temperatures, catalysts and other conditions) are well-known in the art and reference is made thereto for the purpose of this invention. Additional comonomers which can be polymerized with ethylene include olefin monomers having from 3 to 12 carbon atoms, ethylenically unsaturated carboxylic acids (both mono- and difunctional) and derivatives of such acids such as esters (for example, alkyl acrylates) and anhydrides; monovinylidene aromatics and monovinylidene aromatics substituted with a moiety other than halogen such as styrene and methylstyrene; and carbon monoxide. Exemplary monomers which can be polymerized with ethylene include 1-octene, acrylic acid, methacrylic acid, vinyl acetate and maleic anhydride.
Polyolefins which can be employed in the practice of the present invention for preparing the multilayer laminate structure include polypropylene, polyethylene, and copolymers and blends thereof, as well as ethylene-propylene-diene terpolymers. Preferred polyolefins are polypropylene, linear high density polyethylene (HDPE), heterogeneously- branched linear low density polyethylene (LLDPE) such as DOWLEX™ polyethylene resin (a trademark of The Dow Chemical Company), heterogeneously-branched ultra low linear density polyethylene (ULDPE) such as ATTANE™ ULDPE (a trademark of The Dow
Chemical Company); homogeneously-branched, linear ethylene/a-olefin copolymers such as
TAFMER™ (a trademark of Mitsui Petrochemicals Company Limited) and EXACT™ (a trademark of Exxon Chemical Company); homogeneously-branched, substantially linear ethylene/a-olefin polymers such as AFFINITY™ (a trademark of The Dow Chemical
Company) and ENGAGE® a trademark of DuPont Dow Elastomers of polyolefin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and 5,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers such as PRIMACOR™ (trademark of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENE™ polymers (a trademark of Exxon Chemical Company), and ELVAX™ (a trademark of E.I. DuPont de Nemours & Co.). The more preferred polyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 to 0.99 g/cm’, a weight average molecular weight to number average molecular weight ratio (M,/Mp,) from 1.5 to 3.0, a measured melt index (measured in accordance with ASTM D-1238 (190/2.16)) of 0.01 to 100 g/10 minutes, and an 110/12 of 6 to 20 (measured in accordance with ASTM D-1238 (190/10)).
In general, high density polyethylene (HDPE) has a density of at least about 0.94 grams per cubic centimeter (g/cc) (ASTM Test Method D-1505). HDPE is commonly produced using techniques similar to the preparation of linear low density polyethylenes.
Such techniques are described in U.S. Patents 2,825,721; 2,993,876; 3,250,825 and 4,204,050. The preferred HDPE employed in the practice of the present invention has a density of from 0.94 to 0.99 g/cc and a melt index of from 0.01 to 35 grams per 10 minutes as determined by ASTM Test Method D-1238.
Polymers based on aromatic monomers which can be employed in the practice of the present invention include polystyrene, polymethylstyrene, polyethyistyrene, styrene/methylistyrene copolymer, and styrene/chlorostyrene copolymer.
Polyamides which can be employed in the practice of the present invention include the various grades of nylon, such as nylon-6, nylon-66 and nylon 12.
Adhesive materials which can be employed in the practice of the present invention for preparing the adhesive layer include ethylene vinyl acetate copolymers, ethylene/ethyl acrylic acid ester copolymers, ionomers, modified polyolefins as described in
U.S. Patent 5,443,874, acrylic-based terpolymer adhesives as described in U.S. Patent 3,758,769 and adhesives formed by reacting an epoxy resin and an acidified aminoethylated vinyl polymer as described in U.S. Patent 4,447,494. The more preferred adhesive materials are maleic anhydride grafted polyethylene or polypropylene such as ADMER (trademark of
Mitsui Petrochemicals) adhesive resins, or ethylene-vinyl acetate copolymer resins such as
ELVAX™ (trademark of DuPont). The most preferred adhesive material is ELVAX™ 3175, which is a 6 Melt Index, 28 percent vinyl acetate copolymer. The thickness of the monolayer and multilayer structures of the present invention is variable within wide limits, depending on the contemplated application. in general, the monolayer structure of the present invention has a thickness of from 0.05 to 10 mils, preferably, from 0.2 to 6 mils, most preferably, from 0.4 to 1.8 mils. In general, the multilayer structure of the present invention has a thickness of from 0.05 to 200 mils, preferably from 1 to 100 mils, most preferably, from 2 to 80 mils, with the PVDC polymer layer having a thickness of from 0.005 to 20 mils, preferably from 0.2 to 10 mils, most preferably, from 0.2 to 8.0 mils.
The present invention is illustrated in further detail by the following examples.
The examples are for the purposes of illustration only, and are not to be construed as limiting the scope of the present invention. Ali parts and percentages are by weight unless otherwise specifically noted.
Examples 1-3 and Comparative Examples A and B
The following formulations of a vinylidene chloride copolymer (7.75 weight percent methyl acrylate, 92.25 weight percent vinylidene chloride) prepared using a conventional high intensity blender were employed in the examples:
Example 1
Vinylidene chloride copolymer 95.27 wt.
Epoxidized soybean oil 1.2 wt.%
Glycerol monostearate 2.0 wt.%
Oxidized polyethylene wax 0.18 wt. %
Polyethylene wax 0.45 wt.%
High density polyethylene 0.90 wt.%
Example 2 :
Vinylidene chloride copolymer 96.475 wt. %
Epoxidized soybean oil 1.0 wt. %
Glycerol monostearate 2.0 wt.%
Oxidized PE wax 0.1 wt.%
Polyethylene wax 0.1 wt.%
High Mw silicone/HDPE conc. 0.125 wt.%
Comparative Example A
Vinylidene chloride copolymer 96.27 wt.%
Epoxidized soybean oil 2.2 wt.%
Oxidized PE Wax 0.18 wt.%
PE wax 0.45 wt.%
HDPE 0.90 wt.%
Comparative Example B
Vinylidene chloride copolymer 96.8 wt.%
Epoxidized soybean oil 1.2 wt.%
Glycerol Monostearate 2.0 wt.%
Extrusion Conditions: 9 hour trials, started with a clean system (screw, barrel, and die).
Rate: 42 Ib/hr, 17 RPM, 2.5-inch diameter 21:1 L/D Extruder, monolayer cross-head die.
Barrel Temperatures: 150°C (feed), 155°C (transition), 160°C (meter).
Die temperature: 173°C, Nosepiece: 175°C, Adaptor: 175°C, Feedthroat: 38°C.
Extrusion trials were conducted on clean equipment, and the PVDC formulations extruded for 9 hours each. At the end of the 9 hours, the screw was stopped, and full cooling put on the barrel and die. This froze the polymer in the die without additional degradation. The die was then dis-assembied, and the carbon tended to stick to the polymer when removed from the die. This allowed for a method to compare carbon generation between different PVDC copolymer formulations. The Comparative Example A formulation when extruded for 9 hours gave an outer portion of the die that was totally covered with black carbon. When Examples 1 and 2 formulations were extruded for 9 hours, they both gave an outer surface that was totally clean of carbon. The extrusion trial with the
Comparative Example B formulation was stopped after 2 hours because of poor quality film due to heavy die lines, slough, and a rough surface to the film. This indicates that the external lubricants (for example, oxidized PE wax, PE wax, HDPE, silicone concentrate) are necessary in combination with the GMS.
Barrier Testing
Barrier properties were determined for monolayer blown films (1 to 2 mil) at 23°C and 60 percent relative humidity in accordance with ASTM Method D-3985-81. The barrier property of the film formed from the Example 1 formulation (0.085 cc-mil/100 in®-atm- day) was superior compared to that of the Comparative Example A formulation (0.11 cc- mil/100 in*-atm-day). This improvement in barrier is highly desirable. It is surprising that barrier properties and processing are both improved, because usually, an improvement in processability results in a detrimental effect on barrier properties. This is due to the fact that the improved stability of the GMS-containing formulation was obtained at a reduced ESO level (2.0 percent vs. 1.0 percent). It is known that liquid stabilizers have a detrimental effect on barrier properties.
Thermal Stability
Two-roll mill testing was also performed to compare thermal stability of PVDC copolymer formulations. In this test, 200 g of blended PVDC copolymer was placed on two heated, co-rotating rolls. The polymer then melted due to the heat and shear created within the sample. The time to significant degradation was compared between samples. Testing was done at 180°C roll temperature. The Comparative Example A formulation evolved small
HCL bubbles after 11 minutes. The Example 1 formulation took 13.5 minutes to reach the same level of gassing. This is a further indication of the improved thermal stability provided by the GMS-containing formulation.
Units which are used in the specification and which are not in accordance with the metric system may be converted with the aid of the following conversion factors:
Centipoise x 0.001 = pascal-second 1 mil = 2.54 x 0.001cm. -12- Amended Sheet 14/06/01
Claims (23)
1. A vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is a vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, 2) a glycerol ester and (3) a silicone polymer, the glycerol ester and silicone polymer being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer, and, optionally, an epoxidized processing aid.
2. The composition of Claim 1 wherein the vinylidene chloride polymer is formed from a monomer mixture comprising from 60 to 99 weight percent vinylidene chloride monomer and from 40 to 1 weight percent of a monoethylenically unsaturated comonomer copolymerizable therewith.
3. The composition of Claim 2 wherein the monoethylenically unsaturated monomer is vinyl chloride, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, or methacrylonitrile.
4. The composition of Claim 1 wherein the glycerol ester is glycerol monostearate, glycerol monopalmitate, glycerol monooleate, or the diester or triester thereof.
5. The composition of Claim 1 wherein the glycerol ester is present in an amount of from 0.05 to 10 weight percent, based on the weight of the composition.
6. The composition of Claim 1 wherein the silicone polymer is polydimethyl siloxane, polydimethyldiphenyl siloxane or polymethyl alkyl ary! siloxane.
7. The composition of Claim 1 wherein the silicone polymer is present in an amount of from 0.001 to 5 weight percent, based on the weight of the composition.
8. The composition of Claim 1 wherein the silicone polymer is in the form of a concentrate comprising a carrier polymer.
9. The composition of Claim 8 wherein the carrier polymer is a polyolefin, an oxidized polyolefin, an ethylene vinyl acetate copolymer, or an acrylate copolymer.
10. The composition of Claim 1 wherein the epoxidized processing aid is an epoxidized vegetable oil, epoxidized fatty acid monoester or epoxidized diester.
11. The composition of Claim 10 wherein the epoxidized processing aid is linseed oil, soybean oil, coconut oil, safflower oil, sunflower oil, cotton seed oil, or octyl stearate.
12. A vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, 2) a glycerol ester and (3) a polyolefin, the glycerol ester and polyolefin being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer.
13. The composition of Claim 12 wherein the polyolefin is a high density polyethylene, a polyethylene wax, an oxidized polyethylene wax or a mixture thereof.
14. A monolayer structure comprising a vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is a vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, (2) a glycerol ester and (3) a silicone polymer, the glycerol ester and silicone polymer being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer, and optionally, an epoxidized processing aid.
15. A multilayer structure comprising (1) one or more layers of an organic polymer or a blend of two or more different organic polymers, the organic polymer of one layer being the same as or different from the organic polymer of another layer and (2) one or more layers of a vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is a vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, 2) a glycerol ester and (3) a silicone polymer, the glycerol ester and silicone polymer being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer and optionally, an epoxidized processing aid.
16. The multilayer structure of Claim 15 comprising (1) a first outer layer of the organic polymer or blend of two or more different organic polymers, (2) a core layer of the vinylidene chloride polymer composition and (3) a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer.
17. The multilayer structure of Claim 15 comprising (1) a first outer layer of the vinylidene chloride polymer composition, (2) a core layer of the organic polymer or blend of two or more different organic polymers and (3) a second outer layer of an organic polymer which is the same as or different from the organic polymer of the core layer.
18. The multilayer structure of Claim 15 wherein an adhesive layer is interposed between contiguous layers of the multilayer structure.
19. The multilayer structure of Claim 15 wherein the organic polymer is a polyolefin, a polyamide or a polystyrene.
20. A five-layer or seven-layer structure having (A) one or more layers of a vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is a vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, (2) a glycerol ester and (3) a silicone polymer and, optionally, an epoxidized processing aid, the glycerol ester, silicone polymer and epoxidized processing aid being presentin an amount sufficient to improve the extrudability of the vinylidene chloride polymer and (B) the remaining layers comprising an organic polymer or a blend of two or more different organic polymers, the organic polymer of one layer being the same as or different from the organic polymer of another layer.
21. The five-layer or seven-layer structure of Claim 20 wherein an adhesive layer is interposed between contiguous layers of the structure.
22. A monolayer or multilayer structure comprising a vinylidene chloride polymer composition comprising (1) a vinylidene chloride polymer wherein the major component is a vinylidene chloride monomer and the remainder is one or more monoethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer, (2) a glycerol ester and (3) a polyolefin, the glycerol ester and polyolefin being present in an amount sufficient to improve the extrudability of the vinylidene chloride polymer.
23. A flexible or rigid container comprising the monolayer structure of Claim 14, the multilayer structure of Claim 15 or the monolayer or multilayer structure of Claim 22.
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| US20030215555A1 (en) * | 2002-05-17 | 2003-11-20 | Kraft Foods Holdings, Inc. | Food containers with improved release characteristics |
| GB0304757D0 (en) * | 2003-03-01 | 2003-04-02 | Rexam Med Packaging Ltd | Polymeric films and packages produced therefrom |
| JP4634701B2 (en) * | 2003-07-30 | 2011-02-16 | 株式会社クレハ | Vinylidene chloride resin film, casing for meat paste products, and packaged meat paste products |
| SG156694A1 (en) * | 2004-10-12 | 2009-11-26 | Dow Global Technologies Inc | Plasticizer in alkyl acrylate vinylidene chloride polymer |
| CN101228232B (en) * | 2005-07-28 | 2010-12-15 | 株式会社吴羽 | Polyvinylidene chloride resin composition, biaxially stretched film, and method for producing such biaxially stretched film |
| WO2010025015A1 (en) * | 2008-08-27 | 2010-03-04 | Dow Global Technologies Inc. | Polyvinylidene chloride compositions and their use in monofilament structures |
| JP6339435B2 (en) * | 2014-07-23 | 2018-06-06 | 旭化成株式会社 | Vinylidene chloride resin wrap film |
| JP6567860B2 (en) * | 2015-04-23 | 2019-08-28 | 大同化成株式会社 | Vinylidene chloride resin composition |
| US20200048448A1 (en) * | 2015-08-31 | 2020-02-13 | Dow Global Technologies Llc | Vinylidene chloride polymer compositions and articles comprising the same |
| RU2018109384A (en) * | 2015-08-31 | 2019-09-16 | Дау Глоубл Текнолоджиз Ллк | METHODS FOR PRODUCING VINYLIDENCHLORIDE POLYMER COMPOSITIONS |
| WO2017089562A1 (en) * | 2015-11-27 | 2017-06-01 | Solvay Sa | Vinylidene chloride polymer composition comprising at least one allyl cinnamate |
| CN106147085A (en) * | 2016-08-24 | 2016-11-23 | 安徽顺彤包装材料有限公司 | A kind of insulation packaging material and preparation method thereof |
| CN109206797B (en) * | 2018-08-30 | 2021-01-29 | 佛山晨华新材料有限公司 | Preservative film based on vinylidene chloride-ethylene-acrylonitrile copolymer and preparation method thereof |
| KR102519574B1 (en) * | 2020-09-25 | 2023-04-07 | 에스케이이노베이션 주식회사 | Pvdc-based composite with core-shell structure and method for manufacturing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6030343B2 (en) * | 1980-01-24 | 1985-07-16 | チッソ株式会社 | Vinyl chloride resin composition |
| JPH01299084A (en) * | 1988-05-27 | 1989-12-01 | Toshiba Corp | Thermal transfer recording material |
| JP3523340B2 (en) * | 1994-08-30 | 2004-04-26 | 呉羽化学工業株式会社 | Vinylidene chloride polymer moldings |
| JPH09151290A (en) * | 1995-09-27 | 1997-06-10 | Kureha Chem Ind Co Ltd | Vinylidene chloride polymer composition and its molded item |
-
1999
- 1999-04-28 AU AU37689/99A patent/AU750893B2/en not_active Ceased
- 1999-04-28 EP EP99920115A patent/EP1084189A1/en not_active Withdrawn
- 1999-04-28 NZ NZ507945A patent/NZ507945A/en unknown
- 1999-04-28 CN CN99807319A patent/CN1305510A/en active Pending
- 1999-04-28 WO PCT/US1999/009225 patent/WO1999058603A1/en not_active Application Discontinuation
- 1999-04-28 ID IDW20002337A patent/ID28099A/en unknown
- 1999-04-28 BR BR9910684-1A patent/BR9910684A/en not_active IP Right Cessation
- 1999-04-28 JP JP2000548401A patent/JP2002514672A/en active Pending
- 1999-04-28 KR KR1020007012621A patent/KR20010043523A/en not_active Application Discontinuation
- 1999-04-28 CA CA002331495A patent/CA2331495A1/en not_active Abandoned
- 1999-05-12 AR ARP990102240A patent/AR019292A1/en not_active Application Discontinuation
-
2000
- 2000-11-08 ZA ZA200006429A patent/ZA200006429B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2331495A1 (en) | 1999-11-18 |
| NZ507945A (en) | 2003-02-28 |
| WO1999058603A1 (en) | 1999-11-18 |
| ID28099A (en) | 2001-05-03 |
| EP1084189A1 (en) | 2001-03-21 |
| JP2002514672A (en) | 2002-05-21 |
| BR9910684A (en) | 2001-01-09 |
| AU3768999A (en) | 1999-11-29 |
| KR20010043523A (en) | 2001-05-25 |
| AR019292A1 (en) | 2002-02-13 |
| CN1305510A (en) | 2001-07-25 |
| AU750893B2 (en) | 2002-08-01 |
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