CN104470986A - 双轴拉伸制品 - Google Patents
双轴拉伸制品 Download PDFInfo
- Publication number
- CN104470986A CN104470986A CN201380028745.2A CN201380028745A CN104470986A CN 104470986 A CN104470986 A CN 104470986A CN 201380028745 A CN201380028745 A CN 201380028745A CN 104470986 A CN104470986 A CN 104470986A
- Authority
- CN
- China
- Prior art keywords
- starch
- thermoplastic
- goods
- phase
- compatilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920002472 Starch Polymers 0.000 claims abstract description 107
- 239000008107 starch Substances 0.000 claims abstract description 107
- 235000019698 starch Nutrition 0.000 claims abstract description 107
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 70
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 70
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 54
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229920000098 polyolefin Polymers 0.000 claims abstract description 38
- -1 polyene hydrocarbon Chemical class 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 57
- 239000004215 Carbon black (E152) Substances 0.000 claims description 45
- 229930195733 hydrocarbon Natural products 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 16
- 239000011118 polyvinyl acetate Substances 0.000 claims description 16
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000007127 saponification reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229920001059 synthetic polymer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004902 Softening Agent Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920000881 Modified starch Polymers 0.000 description 6
- 239000004368 Modified starch Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 235000019426 modified starch Nutrition 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 5
- 229920000945 Amylopectin Polymers 0.000 description 4
- 229920000856 Amylose Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009795 derivation Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920005844 ecoflex® F Blend C1200 Polymers 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920006348 thermoplastic styrenic block copolymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001866 very low density polyethylene Polymers 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2317/00—Animal or vegetable based
- B32B2317/20—Starch
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- 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
- B32B2323/00—Polyalkenes
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- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
-
- 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
-
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物包含:包含至少一种聚烯烃的聚烯烃相,包含热塑性淀粉的淀粉相,和至少一种相容剂,其中该制品具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。
Description
本发明涉及通过在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物包含含至少一种聚烯烃的聚烯烃相、含热塑性淀粉的淀粉相、和至少一种相容剂。
随着对可持续性和环境的日益重视,对开发源自或包含生物可再生衍生组分的聚合材料的研究相应增加。迄今为止,开发这类聚合材料的大量研究集中在利用天然存在的生物聚合物如淀粉。淀粉有吸引力之处在于其源自于可再生资源(即植物产品),易于获取并且相对廉价。然而,相比于石油衍生(即“合成的”)聚合物的机械性能,天然形式的淀粉的机械性能较差。淀粉的机械性能可通过使其与增塑剂如多元醇熔融混合从而形成热塑性淀粉(有时缩写为TPS)而得以改进。然而,热塑性淀粉改进的机械性能与合成聚合物的机械性能相比仍然相对较差。因此,并不认为热塑性淀粉是石油衍生聚合物的可行替代品。
为了获得淀粉和石油衍生聚合物的益处,对开发聚烯烃和热塑性淀粉的共混物进行了相当数量的研究。然而,实践证明将相对亲水的淀粉与疏水的聚烯烃进行合并以制得具有良好机械性能的共混物是困难的。特别地,将淀粉或TPS与聚烯烃进行熔融加工通常导致形成具有多相不连续形态的共混物。
WO2010/012041公开了一种包含具有小于0.905g/cm3密度的极低密度聚乙烯、乙烯丙烯酸共聚物和热塑性淀粉和/或其组成组分的组合物。发现上述组合物作为共混物表现出聚合物组分之间的优良相容性,和可以用来提供显示出优良性能的聚合物产品。发现熔融加工的聚合物组合物显示出所需性质如低湿气灵敏度、适于印刷的表面、高淀粉含量、优良的机械性能如%伸长率。据信这些所需性质至少部分归功于组合物提供高度相容形式的热塑性淀粉和聚乙烯组分的能力。在该发明的一些实施方案中,据信TPS和聚乙烯组分可以形成稳定的共连续相形态。
US2012/0009387公开了一种挠性聚合物膜,其包含约5%到约45%的热塑性淀粉、约55%到约95%的聚烯烃或聚烯烃混合物、和约0.5%到约8%的相容剂,该相容剂具有非极性主链和极性官能单体,或者非极性嵌段和极性嵌段的嵌段共聚物,或者极性单体和非极性单体的无规共聚物。该膜中的热塑性淀粉以颗粒形式掺入。
CA2,060,650公开了一种基本上降低气体透过性的单层或多层箔,其包含至少一个至少部分由基本上热塑性淀粉组成的层。为了该单层或多层膜对湿气至少接近不敏感,建议至少一层进一步包含至少一种疏水聚合物如聚烯烃,其在生产所述至少一个层时与该淀粉混合,和/或该淀粉至少部分地在所述至少一个层的表面上交联,和/或所述至少一个层被至少一个对湿气至少接近不敏感的另外的层覆盖。
WO2009/022195公开了包含聚烯烃、相容剂、淀粉和增塑剂的组合物。所述组合物可以用来制造膜材料。
US6,605,657公开了一种包含热塑性淀粉和合成聚合物的共连续共混物的物质组合物,其中所述共连续共混物包含热塑性淀粉相和合成聚合物相的混合物,和其中当分别考虑时,热塑性淀粉和合成聚合物相基本上分别由热塑性淀粉和合成聚合物的互连域的网状物组成,和其中所述组合物基本上无水。该合成聚合物可以是聚乙烯。
WO2011/009165公开了一种包含至少三层结构的多层膜,所述三层结构由介于两个覆盖聚合物层之间的芯聚合物层组成,各所述覆盖聚合物均包含聚乙烯,其中该芯聚合物层包含聚乙烯、热塑性淀粉、和乙烯丙烯酸共聚物的熔融共混物。
US5,415,827公开了一种改进单层或多层片材的品质和特别是机械性能的方法,其中至少一层由至少部分基本上无水的可热塑性加工淀粉组成,其是基本上无水的淀粉和添加剂的熔融混合物产品,该添加剂具有超过15cal1/2cm-3/2的溶解度参数、在淀粉/添加剂混合物的熔程中低于1巴的蒸气压,和该添加剂降低了该淀粉的熔点以致该淀粉/添加剂混合物的熔点低于该淀粉的分解温度,其特征在于在生产该片材至少至其基本上不含水之前或期间干燥用来形成该层的材料,生产所述片材,然后单轴或双轴拉伸所生产的片材。该包含淀粉的层可以由可热塑性加工淀粉的基本上几乎全部组成,或者由包含可热塑性加工淀粉和至少一种聚烯烃如聚乙烯或聚丙烯、和优选嵌段共聚物形式的成相剂或粘合剂的聚合物共混物组成。生产这些单层或多层片材之后,单轴或双轴拉伸它们,其可以在室温进行拉伸。
US2008/0182113公开了一种包含生物聚合物、烯烃共聚物,和任选的聚合物的组合物。该生物聚合物可以是改性淀粉,和以基于组合物干重计至少85%的量存在。该烯烃共聚物可以是乙烯和马来酸酐的共聚物。该任选的聚合物包括乙烯共聚物、聚乙烯醇缩丁醛共聚物、或其组合;该乙烯共聚物包括乙烯(甲基)丙烯酸烷基酯聚合物、乙烯乙酸乙烯酯共聚物、乙烯酸共聚物或其离子聚合物、聚(乙烯醇)、聚(羟基链烷酸)、聚酯、聚酰胺、聚氨酯、聚烯烃、聚己酸内酯、共聚醚酯、聚环氧烷、或其中两种或更多种的组合。该组合物可以通过挤出形成膜和片材来制备流廷和吹塑膜。
本发明的目的是提供制品形式的热塑性组合物,该制品具有包含淀粉和聚烯烃的层的多层结构,该制品可以直接由所述热塑性组合物制得,即该制备不需要共挤出或层压该多层。
本发明进一步的目的是提供双轴拉伸的制品,其显示出可印刷性、低氧渗透性、低水蒸气渗透性和可接受的机械性能中至少一些的所需组合。
本发明更进一步的目的是提供具有热塑性淀粉层和聚烯烃层的多层膜,该层不剥离。
本发明特别的目的是提供显示出低氧渗透性和低水蒸气渗透性的组合的双轴拉伸制品。
就此程度而言,本发明涉及通过在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物包含:
-包含至少一种聚烯烃的聚烯烃相,
-包含热塑性淀粉的淀粉相,
-至少一种相容剂,
其中该制品具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。本领域技术人员将理解,因为制品由热塑性组合物获得,实际上是拉伸后的热塑性组合物具有分层形态,因此换言之,本发明涉及通过在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物包含:
-包含至少一种聚烯烃的聚烯烃相,
-包含热塑性淀粉的淀粉相,
-至少一种相容剂,
其中该热塑性组合物在拉伸后具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。
不同于现有技术,本发明提供了热塑性淀粉聚烯烃的多层结构,而不需要多层层压或共挤出步骤。本发明制品的性能类似于或者甚至超过已知的多层材料。
特别地,本发明人发现,由于分层形态,本发明的制品可以提供低氧渗透性和低水蒸气渗透性的所需组合。这种组合不能由聚烯烃如此得到。例如,已知聚乙烯具有较低的水蒸气渗透性,然而氧渗透性太高。对于一些应用,需要聚乙烯是多层箔的一部分,这不太成本有效。此外,本发明制品中的热塑性淀粉含量引入更大的极性,导致更低的表面张力,就可印刷性而言这是所需性能。因此,本发明的制品避免、或者至少降低在印刷前表面处理该制品的需要。本发明人进一步发现,该制品显示出可接受的机械性能,本发明人将这主要归因于至少一种相容剂的存在,该相容剂提高了淀粉相和聚烯烃相之间的结合。
因此,本发明的制品满足上述目的中的至少一些。
本文所用的术语“具有交替层的分层形态”用来表示这样的形态:其中观察到淀粉相和聚烯烃相的层在MD和TD上看处于交替层叠形式和其中该层在纵向和横向上伸展,意味着聚烯烃和热塑性淀粉的层形成在纵向和横向上看基本上连续的层,和在所述方向上不是仅分离区域的组合。
不过,本领域技术人员将会理解,在生产本发明制品期间仍然可以形成热塑性淀粉和/或聚烯烃的一些分离区域。然而,这种分离区域会形成本发明制品的小部分,一般量少于几个重量百分数,例如少于5wt%、优选少于3wt%、更优选少于1wt%。理想地,不存在淀粉相和/或聚烯烃相的分离区域,和各个层在纵向和横向上均是连续的。
在一个实施方案中,本发明涉及通过在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物由以下组成:
-包含至少一种聚烯烃的聚烯烃相,和
-包含热塑性淀粉的淀粉相,和
-至少一种相容剂,
其中,该制品即被拉伸后的热塑性组合物,具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。
在优选的实施方案中,用于生产本发明制品的热塑性组合物包含10-70wt%的至少一种聚烯烃、10-70wt%的热塑性淀粉和5-40wt%的至少一种相容剂。
不希望束缚于此,本发明人相信为了得到具有淀粉相和聚烯烃相的交替层的分层形态,需要获得聚烯烃相的类型、数量和性能,淀粉相的类型、数量和性能与相容剂的类型、数量和性能的平衡。除此之外,还需要纵向和横向拉伸该热塑性组合物到一定程度。
因此,在本发明的优选实施方案中,该热塑性组合物包含重量比为0.8-1.2、优选0.9-1.1、更优选0.95-1.05的聚烯烃相和淀粉相。本发明人注意到,超出这些范围,仍然可能是分层形态。
优选横向拉伸比至少是1.5、优选至少是2,该横向拉伸比定义为:
和/或纵向拉伸比至少是2,该纵向拉伸比定义为:
其中
SRmd=纵向拉伸比
SRtd=横向拉伸比
W0=横向拉伸之前热塑性组合物的宽度[mm]
W1=双轴拉伸制品的宽度[mm]
T0=纵向和横向拉伸之前热塑性组合物的厚度[mm]
T1=双轴拉伸制品的厚度[mm]
还可以根据用来拉伸的方法的特性来定义纵向拉伸比。例如在膜吹塑方法中,纵向拉伸比可以定义为膜卷收盘的速度与热塑性组合物离开挤出模头的速度之间的比。
在更优选的实施方案中,纵向拉伸比和横向拉伸比均至少是2。
优选纵向拉伸比至多是20、更优选至多是15、更加优选至多是10。横向拉伸比优选至多是4。
为了避免疑义,将理解根据定义如本文所定义的拉伸比为大于1,即需要在纵向和横向都拉伸该热塑性组合物。同样地,根据定义″双轴拉伸″制品是指经过在纵向和横向拉伸的制品。拉伸在热塑性组合物处于升高的温度时进行,并且对于获得本发明制品的分层形态是必要的。纵向和横向拉伸一般同时进行。
考虑到淀粉相,被拉伸时热塑性组合物的温度不可以太高,这是因为太高的温度会导致热塑性淀粉发生黄变或褐变。在太高的温度热塑性淀粉还可能变脆,这是不希望的。可行的上限是130℃。拉伸温度的下限在某种程度上取决于热塑性组合物,但是通常来说该下限由聚烯烃相的熔融和结晶温度决定。可行的下限可以是100℃,不过本领域技术人员通过常规实验可以容易地发现可行的下限。优选在高于热塑性淀粉和聚烯烃的熔点的温度对热塑性组合物进行拉伸。
本发明不局限于特定的拉伸方法,然而优选使用膜吹塑技术,因为该技术非常适合于生产膜。然而,还可以应用其他拉伸技术如压延法。本发明不排除注射模塑法来生产本发明制品本身,不过条件是纵向和横向拉伸热塑性组合物。为了成功地生产本发明的制品,需要考虑注射模塑法的更多变量。
优选淀粉相的粘度使其具有根据ISO 1133在130℃的温度和10kg的载荷下测得的2-20g/10min、优选4-10g/10min的熔体流动指数(MFI)。
优选聚烯烃相的粘度使其具有根据ISO 1133在130℃的温度和10kg的载荷下测得的2-20g/10min、优选4-10g/10min的熔体流动指数(MFI)。
聚烯烃相的MFI与淀粉相的MFI之比优选为0.5-1.5、优选0.7-1.3、更优选0.9-1.1,MFI均根据ISO 1133在130℃的温度和10kg的载荷下测得。本发明人注意到,该比越接近1,越容易得到本发明制品的分层形态。
本文使用的术语“相容剂”定义为与淀粉相和聚烯烃相均具有亲合力的材料,该材料能够改进两个相在界面的粘合力,从而热塑性相和聚烯烃相可以共存于同一制品中,而各相不会发生物理分离。因此,在淀粉相和聚烯烃相为层形式的本发明制品中,该层彼此粘附良好并且不易剥离。不打算束缚于此,本发明人相信没有相容剂,淀粉相和聚烯烃相之间界面的表面张力将会过高,而且结果是热力学将是使两相之间的接触表面积最小化的驱动力,这与形成在纵向和横向上伸展的层相反,其本质上会产生显著的接触表面积。由于其特性,相容剂会主要存在于淀粉相和聚烯烃相之间的界面。取决于相容剂的类型,一部分相容剂可以主要存在于聚烯烃相中,而另一部分可以主要存在于淀粉相中。该类型相容剂的例子是具有极性和非极性嵌段的嵌段共聚物。可选地,相容剂主更存在于淀粉相或聚烯烃相中,并且在两相之间的界面处仅与聚烯烃相或淀粉相(视情况而定)接触或与之结合。该类型相容剂的例子是马来酸酐接枝的聚烯烃。本领域技术人员将会理解,相容剂不会在双轴拉伸制品中形成单独的相。
由于聚烯烃相的非极性特性和淀粉相的极性特性,相容剂可以是具有非极性主链和嵌入该主链或接枝其上的极性基团的聚合物材料。该极性基团可以与淀粉具有反应性,并且与至少一部分淀粉反应。相容剂还可以是具有非极性和极性单体的嵌段的嵌段共聚物。
适合的相容剂是乙烯丙烯酸共聚物,乙烯乙酸乙烯酯共聚物,具有接枝其上的至少1wt%马来酸酐的聚烯烃,乙烯乙烯醇共聚物,嵌段皂化的聚乙酸乙烯酯,乙烯、丙烯酸丁酯和马来酸酐的无规三元共聚物,无规、部分水解和皂化的聚乙酸乙烯酯,或者这些相容剂中至少两种的混合物。
部分水解和皂化的聚乙酸乙烯酯可以通过US6,958,369公开的方法得到,该方法包括所公开的变化,其明确并入本文作为参考。该部分水解和皂化的聚乙酸乙烯酯通过以下得到:在催化添加低分子量有机单、二和三羟基化合物(例如甲醇、乙醇、乙二醇、甘油)的存在下,连续添加碱性反应性化合物和碱金属硅酸盐,以水解和皂化聚乙酸乙烯酯。更详细地,生产部分水解和皂化的聚乙酸乙烯酯的方法可以包括以下步骤:
a)提供聚乙酸乙烯酯的水性分散体;
b)向该水性分散体添加选自单羟基化合物、二羟基化合物和三羟基化合物的催化剂;
c)任选地,通过向聚乙酸乙烯酯的水性分散体添加碱性物质,来预皂化该水性分散体;
d)提供碱金属硅酸盐溶液;
e)在分批混合器中,通过在搅拌的同时在至少一小时期间内向步骤c)的预皂化的聚乙酸乙烯酯添加碱金属硅酸盐溶液,以使步骤c)的预皂化的聚乙酸乙烯酯与步骤d)的碱金属硅酸盐溶液反应以形成有机硅酸盐,其中预皂化的聚乙酸乙烯酯和碱金属硅酸盐溶液的合计水含量大于40%。
优选在步骤c)中,连续添加碱性物质直到达到10%到40%的水解度,和其中在步骤e)中,反应进行到达到30%到85%的最终水解度。
优选在步骤c)中,该碱性物质是氢氧化钙,将其添加到达到10%到40%的预皂化度。
相容剂的量优选是基于热塑性组合物的15-30wt%。
用于本发明制品的热塑性淀粉可以由任何适合的淀粉源如谷物、木薯、玉米、小麦、稻米、马铃薯、大豆或这些淀粉源中至少两种的任意组合制成,因为其可得性优选马铃薯淀粉。
本领域技术人员将会理解,热塑性淀粉是包含一种或多种增塑剂的淀粉的变性形式。因此,为了避免疑义,应当理解由淀粉制备热塑性淀粉所需的加工助剂如增塑剂,被认为是热塑性淀粉的一部分。淀粉主要存在于植物的种子、果实、块茎、根和茎髓中,并且是由通过糖苷键在1-4碳的位置连接的重复葡萄糖基团组成的天然衍生聚合物。淀粉主要由直链淀粉(具有约1×105分子量的基本上线性的聚合物)和支链淀粉(具有1×107级别的非常高分子量的高度支化聚合物)组成。
各重复葡萄糖单元一般具有三个自由羟基,由此提供具有亲水性质和反应性官能团的聚合物。大部分淀粉包含20到30%的直链淀粉和70到80%的支链淀粉。然而,取决于淀粉的来源,直链淀粉与支链淀粉的比变化很大。例如,一些谷物杂交种提供具有100%支链淀粉的淀粉(蜡质种玉米淀粉),或者从50到95%逐渐增高的直链淀粉含量。
除了天然形式的淀粉以外,化学改性淀粉也可以用于本发明。化学改性淀粉包括但不限于氧化淀粉、醚化淀粉、酯化淀粉或所述化学改性的组合(例如醚化和酯化淀粉)。适合的醚化淀粉包括但不限于由乙基和/或丙基取代的淀粉。适合的酯化淀粉包括但不限于由乙酰基、丙酰基和/或丁酰基取代的淀粉。
化学改性淀粉通常通过淀粉的羟基与一种或多种试剂反应制得。与对应的天然淀粉相比,通常称为取代度(DS)的反应度可以显著改变改性淀粉的生理化学性能。天然淀粉的DS指定为0,和对于完全取代的改性淀粉可以达到3。取决于取代基类型和DS,相对于天然淀粉,化学改性淀粉可以显示出相当不同的亲水/疏水的特性。
天然淀粉和化学改性淀粉通常均显示出较差的热塑性。为了改善所述性能,可将淀粉转变成热塑性淀粉。例如,天然淀粉或化学改性淀粉可以与一种或多种增塑剂一起熔融加工。多元醇可以用作制造热塑性淀粉中的增塑剂。
热塑性淀粉还通常包含一种或多种多元醇增塑剂。适合的多元醇包括但不限于甘油、乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、聚乙二醇、聚丙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,5-己二醇、1,2,6-己三醇、1,3,5-己三醇、新戊二醇、三羟甲基丙烷、季戊四醇、甘露糖醇、山梨糖醇,和其乙酸酯、乙氧基化物和丙氧基化物衍生物。
在一个实施方案中,热塑性淀粉包含甘油和/或山梨糖醇增塑剂。相对于淀粉和增塑剂组分的总质量,热塑性淀粉的增塑剂含量通常是约5wt%到约50wt%,例如从约10wt%到约40wt%或约10wt%到约30wt%。
虽然本发明主要涉及使用淀物作为制品的组分,但是本发明人不排除使用面粉代替淀粉,淀粉是面粉的主要成分。
本发明制品中的聚烯烃优选选自丙烯均聚物、乙烯丙烯共聚物、聚乙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯和前述聚烯烃中至少两种的混合物。优选聚烯烃的密度至少是0.910g/cm3。为了避免疑义,本领域技术人员将会理解聚烯烃相不局限于同相材料,而是聚烯烃相还可以是异相,例如当乙烯丙烯共聚物分散在丙烯均聚物中时。在一个优选实施方案中,聚烯烃是聚乙烯,特别是低密度聚乙烯或LDPE。
在一个实施方案中,热塑性组合物进一步包含基于热塑性组合物计量为20-60wt%的热塑性聚酯,优选聚(对苯二甲酸丁二醇酯-共-己二酸酯)。该实施方案中优选的相容剂是如US6,958,369公开的部分水解皂化的聚乙酸乙烯酯。
该聚酯可以与热塑性淀粉形成共连续形态,从而在该实施方案中淀粉相将会包含热塑性淀粉、热塑性聚酯和至少部分相容剂。据信该实施方案产生较低极性的淀粉相,这使得与非极性聚烯烃相的相容更容易。为了进一步改进在包含热塑性聚酯的淀粉相与聚烯烃相之间粘着力,优选热塑性组合物包含另外的相容剂,其是聚烯烃,优选具有接枝其上的至少1wt%和优选至多10wt%的马来酸酐的聚乙烯。在另一实施方案中,热塑性淀粉和热塑性聚酯没有形成共连续结构,但是当纵向和横向拉伸时,热塑性聚酯将形成在前述方向上伸展的层,类似于聚烯烃相形成的层。在该特定实施方案中,因比该制品包含以无规但交替的方式层叠的三个层。例如,热塑性淀粉相的层可以被热塑性聚酯的层覆盖,其又被聚烯烃相的层覆盖。可选地,热塑性淀粉相的层可以被聚烯烃相的层覆盖,其又被热塑性聚酯的层覆盖。
优选本发明制品为膜,其具有优选2-250μm厚度和根据ASTM 882测得的至少50MPa的模量和根据ISO 527-3测得的至少200%的断裂伸长率。
本发明的制品,特别是膜,优选具有至多50、更优选至多25、最优选至多10(g·mm/m2·day)(cm3·mm)/(m2·day)的氧气渗透系数,其根据ASIM D-3985(23℃,0%的RH,100%的O2)在具有50-150μm厚度的膜上测得。
本发明的制品,特别是膜,优选具有至多50、更优选至多25、最优选至多10(g·mm/m2·day)的水蒸气渗透系数,其根据ASTM F-1249(38℃,100%的RH)在具有50-150μm厚度的膜上测得。
本发明进一步涉及包含膜形式的本发明制品的多层膜,其具有至少一种另外的合成膜,该合成膜为在纵向和横向上伸展的合成聚合物的合成膜。在这种多层膜的优选实施方案中,膜形式的本发明制品的上侧和下侧均具有合成膜。该合成聚合物优选是聚烯烃,如聚乙烯。可以通过在纵向和横向拉伸之前或之后层压或共挤出,将这种另外的合成膜提供在本发明制品上。
本发明的制品可以通过以下来生产:提供包含至少一种聚烯烃、热塑性淀粉和至少一种相容剂的热塑性组合物,和将所述热塑性组合物进料至挤出机,通过挤出模头挤出该热塑性组合物,和当离开挤出模头时在升高的温度纵向和横向拉伸该热塑性组合物。在该实施方案中,热塑性组合物优选以热塑性组合物的粒料形式进料至挤出机,该粒料在生产制品的方法之前,在单独挤出加工中制备。可选地,该制品可以通过以下来制备:将聚烯烃或者两种或多种聚烯烃的混合物、淀粉、至少一种用于制备热塑性淀粉的加工助剂和至少一种相容剂进料至挤出机,在使得在挤出机中形成包含至少一种聚烯烃、热塑性淀粉和至少一种相容剂的热塑性组合物的条件下挤出这些组分,和当经由挤出模头离开挤出机时在升高的温度纵向和横向拉伸该热塑性组合物。
本发明人注意到,如果使用两步法制备本发明的制品,其中在第一步中生产热塑性组合物的粒料,和其中在第二步中将该粒料进料至用于将所述粒料加工成制品的装置中,该粒料可以显示出或多或少的淀粉相和聚烯烃相的共连续结构(形态)。一些粒料还显示出淀粉相和聚烯烃相的一些交替层。
用于本发明方法的淀粉优选原样使用,并且在被加工成热塑性淀粉之前没有经过干燥或以其他方式处理。
挤出加工期间的温度优选不超过180℃、更优选不超过160℃。当离开挤出模头时,热塑性组合物优选至多130℃。
本发明进一步涉及热塑性组合物,其包含:
-10-70wt%的聚烯烃,优选聚乙烯、更优选低密度聚乙烯(LDPE),
-10-70wt%的热塑性淀粉,
-5-40wt%的至少一种相容剂,其是如本文公开的部分水解和皂化的聚乙酸乙烯酯,
-20-60wt%的热塑性聚酯,优选聚(对苯二甲酸丁二醇酯-共-己二酸酯),
所有重量百分数基于组合物的总重量计。
所述热塑性组合物的优选实施方案,当可应用时,与本文公开的本发明制品的优选实施方案相似。
现在通过以下非限制性的附图和实施例进一步解释本发明。
图1显示了本发明制品的分层形态的模型。
图2示意地显示了生产本发明制品的方法。
图3a到3h分别显示了在纵向和横向上的实施例I到VIII的SEM照片。
图1是本发明的双轴拉伸制品1的示意图。纵向表示为MD,横向表示为TD,和厚度方向表示为Z。从图1清楚地看出,层2、3在纵向和横向上伸展。用附图标记2表示的层代表聚烯烃相,而用附图标记3表示的层代表淀粉相。可以清楚地看出,层2和层3交替,即聚烯烃相层2和淀粉相层3以交替的方式层叠。层2、3的数目主要取决于制品的拉伸比、厚度和热塑性组合物。制品1,不按比例,显示五个层2、3,但是本领域技术人员应该理解,本发明的制品1不限于所述层数。在图1中,显示外层(即在层叠的顶部和底部的层)是聚烯烃层。然而,本发明人已经确定所述外层还可以是热塑性淀粉层。
通过电子显微技术,本发明人已经确定淀粉相的层厚度(即Z方向上的厚度)可以是0.1-50μm,和聚烯烃层的厚度可以是0.1-50μm。优选层至多20μm、更优选至多10μm。
图2示意地显示了纵向和横向拉伸以生产本发明的制品。将具有在横向上的一定宽度、在纵向(MD)上的一定长度和在厚度方向上的厚度的体积元件4双轴拉伸,这意味着将它纵向和横向拉伸。由于纵向和横向拉伸,在厚度方向Z上的厚度将会降低。本发明的制品1不是泡沫,因此当纵向和横向拉伸时,体积元件4的密度基本上不变。在通过膜吹塑制造本发明制品的实施方案中,纵向拉伸比等于吹塑膜的卷收速度与挤出物离开挤出模头的速度之比。在US5,082,616中这被定义为“牵伸(draw down)”比。
实施例I-XII
在下文表1中可以发现实施例I-XII的综述。
图3a到3h显示了在纵向(MD)和横向(TD)上实施例I到VIII的SEM照片。
聚酯是Ecoflex F blend C1200,可商购自BASF,MFI在190℃和2.16kg下为2.4到4.5g/10min。LDPE是Nexcoat 5,可商购自SABIC,具有根据ISO1133在190℃到2.16kg下测得的约5g/10min的MFI和具有约919kg/m3的密度。相容剂是部分(+/-40%)水解和皂化的聚乙酸乙烯酯。天然淀粉购买自Ems landGroup。
另外的添加剂概括在“其他”部分。
通过将所述组分进料到双螺杆共旋转挤出机的第一区来制备形成本发明制品基础的热塑性组合物。在80rpm的螺杆速度和60-110Nm的扭矩下,挤出机的温度分布是30-60-110-160-160-110℃。在聚烯烃开始熔融之前,在挤出机的第一区中形成热塑性淀粉。为了避免淀粉降解和/或黄变,将包括挤出模头的挤出机的最后一区的温度降至110℃。将淀粉原样使用,即在进料至挤出机之前没有经过干燥或以其他方式处理。
利用纵向拉伸比为2和横向拉伸比为6,通过已知方法将热塑性组合物吹塑成膜。
实施例I、III、IV和VII均显示出分层形态,其中本发明人注意到实施例VII的形态与实施例I、III和IV相比显示出有些不规则。本发明人怀疑在制备用于SEM分析期间样品受到破坏。
实施例I和IV均显示出良好的氧气和水蒸气渗透率值。尽管具有分层结构,但是实施例III未通过水蒸气测试。本发明人认为,该实施例中LDPE的量过少。因此,主要层由聚酯材料形成,聚酯材料本身具有比LDPE更高的水蒸气渗透性。
实施例VII显示出,即使具有较低量的相容剂,仍然可能得到具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。
表1
实施例XIII、对比例XIV和实施例XV
按照表2的配方进行三个另外的实验。
聚酯与上述实施例I-XII的中相同。实施例XIII的相容剂与上述实施例I-XII中的相同。实施例XV中的相容剂是Lotader 3410,可商购自Arkema。Lotader 3410是乙烯、丙烯酸丁酯和马来酸酐的无规三元共聚物。淀粉购自Avebe。
表2
图4a到4c显示出在纵向(MD)和横向(TD)上实施例XIII、XIV和XV的SEM照片。
关于对比例XIV的图4b显示出不规规结构,其中层剥离。这在纵向(MD)拍摄的图片中最明显。由表2也可推断出对比例XIV的膜的品质较差,这显示出对比例IV的膜的机械性能与实施例XIII和XV相比较差。
Claims (15)
1.在升高的温度纵向和横向拉伸热塑性组合物得到的双轴拉伸制品,所述热塑性组合物包含:
-包含至少一种聚烯烃的聚烯烃相,
-包含热塑性淀粉的淀粉相,
-至少一种相容剂,
其中该制品具有淀粉相和聚烯烃相的交替层的分层形态,所述淀粉相和聚烯烃相的层在纵向和横向上伸展。
2.根据权利要求1所述的制品,其中该热塑性组合物包含:
-10-70wt%的至少一种聚烯烃,
-10-70wt%的热塑性淀粉,
-5-40wt%的至少一种相容剂,
重量百分数基于热塑性组合物的重量计。
3.根据前述权利要求1-2中一项或多项所述的制品,其具有:
至少1.5、优选至少2的横向拉伸比和/或至少2的纵向拉伸比,该横向拉伸比定义为:
该纵向定义为:
其中
SRmd=纵向拉伸比
SRtd=横向拉伸比
W0=横向拉伸之前热塑性组合物的宽度[mm]
W1=双轴拉伸制品的宽度[mm]
T0=纵向和横向拉伸之前热塑性组合物的厚度[mm]
T1=双轴拉伸制品的厚度[mm]
4.根据前述权利要求1-3中一项或多项所述的制品,其中该纵向拉伸比是至多20、优选至多15、更优选至多10,和/或其中该横向拉伸比是至多4。
5.根据前述权利要求1-4中一项或多项所述的制品,其中该相容剂选自乙烯乙酸乙烯酯共聚物,具有接枝其上的至少1wt%马来酸酐的聚烯烃,乙烯乙烯醇共聚物,乙烯丙烯酸共聚物,部分水解和皂化的聚乙酸乙烯酯,乙烯、丙烯酸丁酯和马来酸酐的无规三元共聚物,或者这些相容剂中至少两种的混合物。
6.根据前述权利要求1-5中一项或多项所述的制品,其中淀粉相的MFI为根据ISO 1133在130℃和10kg的载荷下测得的2-20g/10min、优选4-10g/10min。
7.根据前述权利要求1-6中一项或多项所述的制品,其中聚烯烃相的MFI为根据ISO 1133在130℃和10kg的载荷下测得的2-20g/10min、优选4-10g/10min。
8.根据前述权利要求1-7中一项或多项所述的制品,其中聚烯烃相的MFI与淀粉相的MFI之比是0.5-1.5、优选0.7-1.3、更优选0.9-1.1,MFI均根据ISO 1133在130℃和10kg的载荷下测得。
9.根据前述权利要求1-8中一项或多项所述的制品,其中该热塑性组合物进一步包含量为20到60wt%的热塑性聚酯,优选聚(对苯二甲酸丁二醇酯-共-己二酸酯)。
10.根据权利要求9所述的制品,其中相容剂是部分水解和皂化的聚乙酸乙烯酯。
11.根据前述权利要求9-10中一项或多项所述的制品,其中该热塑性组合物包含另外的相容剂,该相容剂为具有接枝其上的至少1wt%和优选至多10wt%的马来酸酐的聚烯烃。
12.根据前述权利要求1-11中一项或多项所述的制品,其中该制品是优选具有2-250μm厚度的膜,所述优选的膜具有根据ASTM 882测得的至少50MPa的模量,和根据ISO 527-3测得的至少200%的断裂伸长率。
13.包含根据权利要求12所述的膜的多层膜,其中所述膜具有至少一种另外的合成膜,该合成膜为在纵向和横向上伸展的合成聚合物的合成膜。
14.生产根据前述权利要求1-13中任一项或多项所述的制品的方法,其包括
-提供包含至少一种聚烯烃、热塑性淀粉和至少一种相容剂的热塑性组合物,和将所述热塑性组合物进料至挤出机,通过挤出模头挤出该热塑性组合物,和当离开挤出模头时在升高的温度纵向和横向拉伸该热塑性组合物,
或者
-将聚烯烃或者两种或更多种聚烯烃的混合物、淀粉、至少一种用于制备热塑性淀粉的加工助剂和至少一种相容剂进料至挤出机,在使得在挤出机中形成包含至少一种聚烯烃、热塑性淀粉和至少一种相容剂的热塑性组合物的条件下挤出这些组分,和当经由挤出模头离开挤出机时在升高的温度纵向和横向拉伸该热塑性组合物。
15.根据前述权利要求1-13中任一项或多项所述的制品作为氧气和水蒸气扩散阻挡层的用途。
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