CN105602215B - A kind of heat-resisting sheet material of biodegrade and preparation method thereof - Google Patents
A kind of heat-resisting sheet material of biodegrade and preparation method thereof Download PDFInfo
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- CN105602215B CN105602215B CN201610054461.6A CN201610054461A CN105602215B CN 105602215 B CN105602215 B CN 105602215B CN 201610054461 A CN201610054461 A CN 201610054461A CN 105602215 B CN105602215 B CN 105602215B
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- heat
- sheet material
- acid
- resisting
- biodegrade
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 30
- 239000004626 polylactic acid Substances 0.000 claims abstract description 30
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000002537 cosmetic Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 14
- 208000016261 weight loss Diseases 0.000 claims description 14
- 230000004580 weight loss Effects 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- -1 succinic acid-butanediol ester Chemical class 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229920001896 polybutyrate Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 230000000655 anti-hydrolysis Effects 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- ILNDSSCEZZFNGE-UHFFFAOYSA-N 1,3-Di-tert-butylbenzene Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1 ILNDSSCEZZFNGE-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 125000006178 methyl benzyl group Chemical group 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims 2
- 241000219198 Brassica Species 0.000 claims 1
- 235000003351 Brassica cretica Nutrition 0.000 claims 1
- 235000003343 Brassica rupestris Nutrition 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims 1
- 235000010460 mustard Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000004513 sizing Methods 0.000 claims 1
- 238000003490 calendering Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- SVUJNSGGPUCLQZ-FQQAACOVSA-N tenofovir alafenamide fumarate Chemical compound OC(=O)\C=C\C(O)=O.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1.O([P@@](=O)(CO[C@H](C)CN1C2=NC=NC(N)=C2N=C1)N[C@@H](C)C(=O)OC(C)C)C1=CC=CC=C1 SVUJNSGGPUCLQZ-FQQAACOVSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a kind of heat-resisting sheet material of biodegrade and preparation method thereof.The heat-resisting sheet material of the biodegrade by weight percentage, including following component：Polylactic acid 20%-50%；PBS 35%-55%；Polyester 0%-10%；It is nucleated reinforcing agent 1%-25%；Auxiliary agent 0.5%-5%, anti-UV agent 0%-0.5%.The current polylactic acid sheet material brittleness of present invention solution is big, thermo-labile and calendered sheet is at high cost, the problems such as application range is narrow, realize that low cost, high efficiency production have the biodegradable sheet material of desirable physical mechanical property, processability and heat resistance, it is widely used in the fields such as electronic product, cosmetics, disposable heat-resisting articles, widens the application range of biodegradable product.
Description
Technical field
The present invention relates to a kind of heat-resisting sheet materials of biodegrade and preparation method thereof.
Background technique
High molecular material has used many decades, brings huge change to people's life, too busy to get away height in life
Molecular material and its product, but polymer material and its waste want centuries that could decompose, and it offers convenience to the mankind
Serious " white pollution " is also brought simultaneously, has become one of the Important Problems of global concern at present.Biodegradable high score
The research and development of son receives national governments and the attention of people, and is considered as the strategic direction of the following new material, and solves
The optimal path of white pollution.But past many years, biodegradation material are mainly answered since technical bottleneck and application field limit
Used in starch base, film class packaging and the fields such as low temperature cold drink, research and development and application in terms of sheet material have that comparison is more, but mainly with poly- cream
Sheet material and part calendered sheet based on acid is modified, it is big that there are brittleness, and aging is fast, resistance to heat differential and it is at high cost the problems such as, with curtain coating
Method prepares biodegradable heat-resisting sheet material and has no relevant successful application at present.
The relevant patent of invention having disclosed of technical solution book related to the present invention and its defect are as follows：
Chinese patent (publication number CN101831086A) proposes the modification sheet material of a kind of starch base and PVA, is used for tableware
Deng, but starch and glycerol used are easy the moisture absorption, are unfavorable for saving, safety and service life are too short；
Chinese patent (publication number CN102352093A) proposes a kind of preparation method of Double-side delustered biodegradable sheet,
There is apparent progress in processing, product appearance and performance, but the blending of polylactic acid and PBAT, calcium carbonate can not solve heat-resisting ask
Topic, product still may be only available for low temperature environment；
A kind of method that Chinese patent (publication number CN102744850A) proposes double-colored biodegradable sheet material, but solve only
Processing problems in terms of color do not propose solution to the heat-resisting of articles of sheet material and other problem of appearance；
Chinese patent (publication number CN101157793A) proposes a kind of preparation method of heat-proof polylactic acid product, but this method
It is realized by the way of mixing, hot-forming and isothermal crystal, heat-resisting sheet material can not be prepared on common sheet former,
Complex process, appropriate products narrow range；
Chinese patent (publication number CN1931907A) proposes a kind of polylactic acid sheet material preparation method, but uses amyloplaste
System, there are critical defects in terms of heat-resisting and hydrolysising aging；
Chinese patent (publication number CN101362853A) proposes a kind of preparation side of recyclable polylactic acid sheet material of low cost
Method, this method provides the method for processing forming of good polylactic acid substrate sheet, but the brittleness of polylactic acid sheet material and thermo-labile
The problem of not can solve, be of limited application；
Chinese patent (publication number CN102977566A) proposes the blending sheet material of PHA/PBS a kind of, in calendering technology and
Obtain significant breakthrough in heat resistance, but PHA is there are at high cost, smell is big, is difficult to the problems such as industrialization, calendered product in cost and
Using etc. be difficult to be commercialized；
Japan Patent (publication number 98122839.9) proposes the preparation method of PBS/PLA/ filler blending and modifying, but main
Applied to zipper and fastener products, and polylactic acid is unable to satisfy the intensity requirement of sheet class product as dispersed phase；
Chinese patent (publication number CN102020773A) proposes and prepares PLA-PBS copolymer with copolymerization mode, but all selects
Fusing point with oligomer, copolymer is low, poor heat resistance, can not bring the promotion of substantive properties of product；
Chinese patent (publication number CN102153846A), which is proposed, prepares PHA/PETG composite sheet with rolling process, solves
The problems such as heat-resisting and processing, but cost is too high and is not used to the application fields such as plastic uptake；
Chinese patent (publication number CN103540111A) discloses a kind of preparation side of the polylactic acid sheet material of high-strength high-temperature resistant
Method, no matter but the method all show intensity from theoretical or actual verification and heat-resisting disclosed numerical value, dependence be all much not achieved
The toughening modifying and filling blend of statement are can not to bring intensity and heat-resisting multiplication effect.
Summary of the invention
There are many research of biodegradable sheet material, but the application in terms of being only capable of mostly as simple non-returnable container, such as poly-
The low temperature Blister product of lactic acid substrate, PBS substrate because too soft fail to be widely applied, and will as institutional packaging product it is complete
It is unable to satisfy the requirement of mechanical property and heatproof entirely.Demand with people to biodegradation material, more and more high-end systems
Product propose the requirement of higher intensity, heat-resisting, durability, appearance etc. to biodegradation material.With excellent mechanical property
The heat-resisting sheet material of biodegrade of energy can satisfy the demand of part-structure outer packing, and in container transport, storage life, power
Intensity etc. is learned to be broken through.
For this purpose, the present invention is in view of the defects existing in the prior art and blank, comprehensive polylactic acid and other biological are degraded polyester
Performance advantage, by formula and technique prepare it is a kind of there is excellent mechanical property, weatherability and heat resistance, and use
Common cast-sheet equipment processing, it is more advantageous in cost.
A kind of heat-resisting sheet material of biodegrade, by weight percentage, including following component：Polylactic acid 20%-50%；
PBS35%-55%；Polyester 0%-10%；It is nucleated reinforcing agent 1%-25%；Auxiliary agent 0.5%-5%, anti-UV agent 0%-0.5%.
Preferably, the polylactic acid is greater than 100,000 middle heavy polymer, polymerization third using molecular weight
Lactide ring-opening polymerisation, low molecular weight lactic acid chain-extension polymerization, one of Pfansteihl or the compound vertical ditch body of D-ALPHA-Hydroxypropionic acid；Wherein, newborn
Acid has L (left-handed type) and D (dextroform), generally L-type polylactic acid, the compound crystallinity that lactic acid can be improved of the two and fusing point.
Preferably, the PBS uses succinic acid-butanediol ester condensation polymer, and molecular weight is greater than 100,000, and carboxyl acid value content is low
In 20mg/mol；The polyester is using at least one of PBAT, PBSA, PHBV and P3HB4HB；The nucleation reinforcing agent uses
One of talcum powder, kaolin, montmorillonite, mica, wollastonite are a variety of.
Preferably, described PBAT, PBSA are that yield strength is at least 7Mpa, and elongation at break is at least 500%, and melting refers to
Number is 5-20g/10min, and terminal carboxyl group acid value content is lower than 20mg/mol；The P3HB4HB is 4HB content 3%-9%, described
PHBV be HV content be 3-10%, the melt index of the PBAT kind polyester is 5-20g/min.
Preferably, the antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters, 2- spy
Butyl -6- (- 5 methylbenzyl of 3- tertiary butyl -2- hydroxyl) -4 aminomethyl phenyl acrylate, phosphorous acid three (2,4- di-t-butylbenzene)
One of ester is a variety of；The lubricant using stearic acid, calcium stearate, zinc stearate, magnesium stearate, barium stearate,
One of EBS, PE wax, TAF, erucyl amide, oleamide, titanate coupling agent and titanium Aluminate composite coupler are several
Kind；
The compatilizer using maleic acid anhydride graft polymers, esters of acrylic acid, glycidyl methacrylate class,
One of peroxide and BASF chain extender are several；
The anti-hydrolysis agent is using carbonization imines；
By total weight ratio, the auxiliary agent includes antioxidant 0.1%-0.25%, lubricant 0.1%-1.5%, compatilizer
0%-3% and anti-hydrolysis agent 0.1%-1.2%.
Polylactic acid used in the present invention is Biodegradable Materials, is derived from plant, can give birth under composting conditions after use
Object is degraded into water and carbon dioxide；With excellent physical mechanics intensity (tensile strength 60MPa), blown film, piece can be widely used for
The application such as material, fiber, injection molding, but there are brittleness big (impact strength≤2j/m, elongation≤5%, poor heat resistance (glass for polylactic acid
Glass temperature is 55-60 DEG C, and Wei Ka and heat distortion temperature are about 55 DEG C), acid and alkali-resistance and resistant to hydrolysis aging are poor, seriously constrain
The application field of polylactic acid；Modification patent about polylactic acid is very much, but the research in heat-resisting sheet applications is fewer
See.
PBS material used in the present invention is poly butylene succinate, is that comprehensive performance is more outstanding in biodegradation material
Kind, tensile yield strength 40MPa or so and PP, ABS etc. quite, heat resistance is good, and HDT temperature changes close to 90 DEG C
Property after using temperature close to 100 DEG C, than other biological degradable material have better heat resistance.Processing performance is very good,
All kinds of processing and formings can be carried out on existing plastic processing common apparatus, be that current degradative plastics processing performance is best, and
And can be blended with various fillers, furthermore PBS can be with producing after existing general purpose polyester scrap build, and cost is cheaper, and
PBS only just degrades under the conditions of the specified microorganisms such as compost, water body, and performance is steady in normal storage and use process
It is fixed.The shortcomings that PBS, is that its crystallinity is high (30%-60%), and physical property is partially crisp.
The other biological degradation polyester material that the present invention uses further comprises PBAT (poly-succinic-terephthalic acid (TPA)-fourth two
Alcohol ester), PBSA (poly-succinic-adipic acid-butanediol ester), polyhydroxyalkanoates (PHB and its copolymer) etc., these are also tool
There is biodegradation character, provides bigger selection for modified product comprehensive performance, be conducive to the application of heat-resisting sheet material
Diversification.
The present invention also provides a kind of methods for preparing the heat-resisting sheet material of biodegrade, including following steps：
Step A:Predrying：Polylactic acid and polyester are pre-dried using dehumidifying device, moisture is reduced to
Within 150ppm；
Step B：Mixing：PLA, PBS and polyester being put into closed high-speed mixer and is mixed, temperature is 20 DEG C -50 DEG C,
It is stand-by to be put into the first weight-loss metering device by time 5-15min after mixing；Nucleation reinforcing agent and auxiliary agent are put into closed high-speed mixer
It is sufficiently mixed, 20-40 DEG C of temperature, time 10-20Min, it is stand-by that the second weight-loss metering device is put into after mixing；
Step C:Plasticizing is kneaded according to proportion, weightless feeder parameter is adjusted, respectively adds major ingredient, powder simultaneously in proportion
Enter into parallel dual-screw extruding machine melt blending, melting temperature is 120 DEG C -180 DEG C, screw speed 100-400rpm；
Step D:It is granulated:The blend being plasticized through double screw extruder is granulated by way of the cooling tie rod pelletizing of water or
Person is prepared into evengranular particle by underwater flour milling pelletizing mode；
Step E:Re-dry:The heat resistance modified resin re-dry of biodegrade for being obtained step D using dehumidifying device, will
Moisture content is reduced within 150ppm；
Step F：Sheet forming：The dried resin that step E is obtained is added in sheet extruder, at 130-210 DEG C
Lower extrusion sheet, sizing cooling by three rollers, obtains heat-resisting sheet material after adjusting dimensions.
Wherein, the mode of the cooling tie rod pelletizing of water refers to that pull out material strip from extruder dries up after cooling is hardened again in the sink
And entering pelleter pelletizing, underwater flour milling pelletizing mode is also the technique being granulated, cutter and porous dies fitting, and cutter rotation will
Enter centrifuge after being water-cooled again after the material cutting that extruder comes out to dry.
Preferably, in step C, temperature is 120 DEG C -165 DEG C, screw speed 180-350rpm.
The present invention also provides a kind of twin-screw mixer extrusion systems for being used to prepare heat-resisting sheet material, including what is set gradually
High-speed mixer, conveyer, resin weight-loss metering device, powder weight-loss metering device, exhaust outlet, twin-screw mixer squeeze out
Unit, cooling trough, hair dryer, pelleter and storage tank, twin-screw mixer screw slenderness ratio are not less than 40：1, it is kneaded gear block
Not less than 7 groups.
Preferably, twin-screw mixer screw slenderness ratio 44：1 or 42：1, being kneaded gear block is 10 groups or 13 groups.
The present invention also provides a kind of forming processing systems for being used to prepare heat-resisting sheet material, including the dry dress set gradually
It sets, drawing-in device, fusion plastification extrusion device, three-roll press-polishing cooling and shaping device, draw cutting means and wrap-up.
The beneficial effects of the invention are as follows：The present invention provides a kind of using the heat-resisting sheet material of common casting technique preparation biodegrade
Method, solve the problems such as current polylactic acid sheet material brittleness is big, thermo-labile and calendered sheet is at high cost, and application range is narrow, it is real
Existing low cost, high efficiency production have the biodegradable sheet material of desirable physical mechanical property, processability and heat resistance, are widely applied
In fields such as electronic product, cosmetics, disposable heat-resisting articles, the application range of biodegradable product is widened.
Detailed description of the invention
Fig. 1 is the twin-screw mixer extrusion system schematic diagram that the present invention prepares heat-resisting sheet material.
Fig. 2 is the forming processing system schematic diagram that the present invention is used to prepare heat-resisting sheet material.
Specific embodiment
With reference to the accompanying drawing, preferably embodiment of the invention is described in further detail：
As shown in Figure 1, a kind of twin-screw mixer extrusion system for being used to prepare heat-resisting sheet material, including the high speed set gradually
Mixing machine 1, conveyer 2, resin weight-loss metering device 3, powder weight-loss metering device 4, exhaust outlet 5, twin-screw mixer are squeezed
Unit 6, cooling trough 7, hair dryer 8, pelleter 9 and storage tank 10 out.
As shown in Fig. 2, a kind of forming processing system for being used to prepare heat-resisting sheet material, including the drying device set gradually
11, drawing-in device 12, fusion plastification extrusion device 13, three-roll press-polishing cooling and shaping device 14, traction cutting means 15 and winding
Device 16.
Embodiment 1
By weight percentage, by 8000 mesh talcum powder 3%, titanium dioxide 2%, PE wax 0.75%, calcium stearate 0.5%, bar
This husband's chain extender 0.5%, 10100.1%, carbonization imines 1.15% place B after 40 DEG C of mixing 20min of high-speed mixer are added
It is spare in number weight-loss metering device, by the P3HB4HB 10% of 4HB content 6%, PBS 37%, after 45% removal moisture drying of polylactic acid plus
Enter to mix 15min under high-speed mixer room temperature and place A weight-loss metering device later, is squeezed simultaneously into twin-screw with B mixture
Machine melt blending out, water stretching and granulation can be used for preparing various sheet materials and other various products.It will be added after the drying of above-mentioned resin
In the sheet extruder for being 130mm to screw diameter, 1.0- is prepared under 160-195 DEG C of extrusion temperature, 40rpm extruded velocity
1.8mm sheet material has excellent appearance and good comprehensive performance.
Embodiment 2
By weight percentage, by 10000 mesh talcum powder 8%, 6000 mesh micas 3%, EBS 0.5%, zinc stearate
0.5%, titanate coupling agent 0.2%, 1,010 0.1%, phosphite ester antioxidant 0.1%, UV527 0.3%, be carbonized imines
It is spare in placement B weight-loss metering device after 0.3%, addition 50 DEG C of mixing 20min of high-speed mixer, by HV content 10%
PHBV5%, PBS 40%, polylactic acid 40%, PBAT2%, which is added under high-speed mixer room temperature, places No. A mistake after mixing 10min
Restatement measuring device enters double screw extruder melt blending with B mixture simultaneously, and water cooling bracing is granulated, can be used for preparing various
Sheet material and other various products.Above-mentioned resin is added to after dry in the sheet extruder that screw diameter is 130mm, in 160-
185 DEG C of extrusion temperatures prepare 0.5-1.65mm sheet material under 30rpm extruded velocity, with excellent appearance and good comprehensive
Close performance.
Embodiment 3
By weight percentage, by 3000 mesh wollastonites 5%, nano montmorillonite 1%, 5000 mesh kaolin 4%,
TAF0.5%, stearic acid 0.5%, titanium Aluminate composite coupler 0.1%, 1,076 0.1%, (2, the 4- di-tert-butyls of phosphorous acid three
Benzene) ester 0.1%, maleic anhydride 0.2%, cumyl peroxide 0.1%, be carbonized imines 0.4%, is added 50 DEG C of high-speed mixer
It is spare in placement B weight-loss metering device after mixing 30min, PBSA 5%, PBS 38% are added after polylactic acid 45% is dry
8min is mixed under high-speed mixer room temperature and places A weight-loss metering device later, enters double screw extruder simultaneously with B mixture
Melt blending, stretching and granulation can be used for preparing various sheet materials and other various products.Screw rod will be added to after the drying of above-mentioned resin
Diameter is to prepare 0.3- under 160-190 DEG C of extrusion temperature, 20-35rpm extruded velocity in the sheet extruder of 130mm
1.2mm sheet material has excellent appearance and good comprehensive performance.
Performance is as shown in table 1, and wherein the modified PLA of comparative example, modified PBS, hard PVC and HIPS buying are in market.
Table 1
As known to table 1, heat-resisting sheet material prepared by the present invention has following performance：
1. having excellent comprehensive strength, it is able to satisfy the packaging intensity requirement of the hard sheets such as most of PS, PVC, PETG,
And maintain good toughness；
2. having good heat resistance, packaging structure part is able to satisfy to heat-resisting requirement；
3. extending weatherability, especially hydrothermal aging, the shelf life of biodegradable sheet material is substantially prolonged；
4. good melt strength, a possibility that having ensured the biodegradable sheet material of molding 1.6mm or more thickness, widen
The application field of biodegradable sheet material；
5. there are the advantages such as yield is big, at low cost, popularization is fast using twin-screw mixer and the production of common sheet former.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (2)
1. a kind of method for preparing the heat-resisting sheet material of biodegrade, which is characterized in that include the following steps：
Step A:Predrying：Polylactic acid and polyester are pre-dried using dehumidifying device, moisture is reduced to 150ppm
Within；
Step B：Mixing：Polylactic acid, PBS and polyester being put into closed high-speed mixer and is mixed, temperature is 20 DEG C -50 DEG C,
It is stand-by to be put into the first weight-loss metering device by time 5-15min after mixing；Nucleation reinforcing agent and auxiliary agent are put into closed high-speed mixer
It is sufficiently mixed, 20-40 DEG C of temperature, time 10-20min, it is stand-by that the second weight-loss metering device is put into after mixing；
Step C:It is kneaded plasticizing:According to proportion, weightless feeder parameter is adjusted, is respectively added to raw material in the same direction simultaneously in proportion
Melt blending in twin-screw extrusion system, melting temperature are 120 DEG C -165 DEG C, screw speed 180-350rpm；
Step D:It is granulated:The blend being plasticized through twin-screw extrusion system is granulated by way of the cooling tie rod pelletizing of water or
Evengranular particle is prepared by underwater flour milling pelletizing mode；
Step E:Re-dry:The heat resistance modified resin row drying again of biodegrade for being obtained step D using dehumidifying device, by water
Point content is reduced within 150ppm；
Step F：Sheet forming：The dried resin that step E is obtained is added in forming processing system, at 130-210 DEG C
Extrusion sheet, sizing cooling by three rollers, obtains heat-resisting sheet material after adjusting dimensions；
A kind of heat-resisting sheet material of biodegrade by weight percentage, including following component：Polylactic acid 20%-50%；PBS 35%-
55%；Polyester 0%-10%；It is nucleated reinforcing agent 1%-25%；0 .5%-5% of auxiliary agent；
The polylactic acid is greater than 100,000 middle heavy polymer using molecular weight, and polymerization is poly- for lactide open loop
It closes, low molecular weight lactic acid chain-extension polymerization, one of Pfansteihl or the compound vertical structure body of D-ALPHA-Hydroxypropionic acid direct polymerization；The PBS is adopted
With succinic acid-butanediol ester condensation polymer, molecular weight is greater than 100,000, and carboxyl acid value content is lower than 20mg/mol；The polyester uses
At least one of PBAT, PBSA, PHBV and P3HB4HB；Described PBAT, PBSA are that yield strength is at least 7MPa, and fracture is stretched
Long rate is at least 500%, and melt index 5-20g/10min, terminal carboxyl group acid value content is lower than 20mg/mol；The P3HB4HB
Be that HV content is 3-10% for 4HB content 3%-9%, the PHBV, the nucleation reinforcing agent using 10000 mesh talcum powder,
5000 mesh kaolin, nano montmorillonite, 6000 mesh micas, 3000 mesh wollastonites it is one or more；It is described to help by total weight ratio
Agent includes 0 .1%-0 .25% of antioxidant, 0 .1%-1 .2% of 0 .1%-1 .5% of lubricant, compatilizer 0%-3% and anti-hydrolysis agent；
The antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters, 2- tertiary butyl -6-（3- is special
- 5 methylbenzyl of butyl-2-hydroxy）- 4 aminomethyl phenyl acrylate, phosphorous acid three（2,4- di-t-butylbenzenes）One of ester or
It is a variety of；The lubricant uses stearic acid, calcium stearate, zinc stearate, magnesium stearate, barium stearate, EBS, PE wax, TAF, mustard
One or more of sour amide, oleamide, titanate coupling agent and titanium Aluminate composite coupler；The compatilizer uses
One of maleic acid anhydride graft polymers, esters of acrylic acid, glycidyl methacrylate class and BASF chain extender
Or it is several；The anti-hydrolysis agent is using carbonization imines；
The Co rotating Twin Screw Extrusion system of the heat-resisting sheet material, high-speed mixer, conveyer, resin including setting gradually lose
Weight formula meter, powder weight-loss metering device, exhaust outlet, twin-screw mixer extruder group, cooling trough, hair dryer, pelletizing
Machine and storage tank, twin-screw mixer screw slenderness ratio are 44：1 or 42：1, being kneaded gear block is 10 groups or 13 groups；
The forming processing system of the heat-resisting sheet material, drying device, drawing-in device, fusion plastification including setting gradually squeeze out dress
It sets, three-roll press-polishing cooling and shaping device, draw cutting means and wrap-up.
2. the heat-resisting sheet material of biodegrade as described in claim 1 answering in electronic product, cosmetics, disposable heat-resisting articles
With.
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| CN110804287A (en) * | 2019-11-11 | 2020-02-18 | 湖南工业大学 | Heat-resistant modified polylactic acid composite material |
| KR102257140B1 (en) * | 2019-12-26 | 2021-05-27 | 주식회사 윤바이오테크 | Biodegradable resin composition, molded article comprising the same, and method for manufacturing the molded article |
| WO2021185339A1 (en) * | 2020-03-19 | 2021-09-23 | 东丽先端材料研究开发（中国）有限公司 | Biodegradable resin and film prepared thereby |
| CN112063125A (en) * | 2020-09-11 | 2020-12-11 | 新疆蓝山屯河高端新材料工程技术研究中心(有限公司) | Special material for preparing full-biodegradable mulching film, full-biodegradable mulching film prepared from special material and preparation method of mulching film |
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| GB202111050D0 (en) * | 2021-07-30 | 2021-09-15 | Chestnut Natural Capital Ltd | Biodegradable plastic composition |
| CN114311914A (en) * | 2021-12-13 | 2022-04-12 | 佛山碧嘉高新材料科技有限公司 | Biodegradable multilayer co-extrusion low-density heat-insulation sheet and preparation method and application thereof |
| CN114163796A (en) * | 2021-12-14 | 2022-03-11 | 杭州晟天新材料科技有限公司 | Full-biodegradable material special for nail beautification and preparation method thereof |
| CN115058783A (en) * | 2022-06-24 | 2022-09-16 | 宁波禾素纤维有限公司 | Raw material co-extrusion device for preparing PHVB and PLA blended bio-based fibers |
| CN115890962B (en) * | 2023-03-09 | 2023-05-23 | 北京蓝晶微生物科技有限公司 | Granulation processing method of low-melt-index degradable material and formed body prepared by same |
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Granted publication date: 20181116 |