CN105602215A - Biodegradable heat-resistant sheet and preparation method thereof - Google Patents
Biodegradable heat-resistant sheet and preparation method thereof Download PDFInfo
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- CN105602215A CN105602215A CN201610054461.6A CN201610054461A CN105602215A CN 105602215 A CN105602215 A CN 105602215A CN 201610054461 A CN201610054461 A CN 201610054461A CN 105602215 A CN105602215 A CN 105602215A
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- Prior art keywords
- heat
- sheet material
- resisting
- biodegradation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000006911 nucleation Effects 0.000 claims abstract description 5
- 238000010899 nucleation Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 61
- 238000006065 biodegradation reaction Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 14
- 208000016261 weight loss Diseases 0.000 claims description 14
- 230000004580 weight loss Effects 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 12
- -1 succinic acid-butanediol ester Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001896 polybutyrate Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 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
- 238000001035 drying Methods 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 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
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000005520 cutting process Methods 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
- 229910052618 mica group 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
- 239000000843 powder Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 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
- 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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-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
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000010445 mica Substances 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
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 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 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 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
- 238000005453 pelletization Methods 0.000 claims 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims 2
- 235000013312 flour Nutrition 0.000 claims 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000003801 milling Methods 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
- 239000004626 polylactic acid Substances 0.000 abstract description 23
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 239000003623 enhancer Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- ILNDSSCEZZFNGE-UHFFFAOYSA-N 1,3-Di-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1 ILNDSSCEZZFNGE-UHFFFAOYSA-N 0.000 description 1
- 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
- ISICZTRAEFADJJ-UHFFFAOYSA-N P(O)(O)O.C(C)(C)(C)C1=CC=CC(=C1)C(C)(C)C Chemical compound P(O)(O)O.C(C)(C)(C)C1=CC=CC(=C1)C(C)(C)C ISICZTRAEFADJJ-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
- 238000013459 approach 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
- 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
- 239000013078 crystal Substances 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment 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
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 150000008301 phosphite esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004017 vitrification Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a biodegradable heat-resistant sheet and a preparation method thereof. The biodegradable heat-resistant sheet is prepared from, by weight, 20-50% of polylactic acid, 35-55% of PBS, 0-10% of polyester, 1-25% of nucleation enhancer, 0.5-5% of an auxiliary and 0-0.5% of an anti-UV agent. The biodegradable heat-resistant sheet and the preparation method solve the problems that existing polylactic acid sheets are high in brittleness, not resistant to heat, high in sheet rolling cost, narrow in application range and the like. The biodegradable sheet is low in cost, can be efficiently produced, has good physical and mechanical properties, machinability and heat resistance, and can be widely applied to the fields such as electronic products, cosmetics and disposable heat-resistance articles. The application range of biodegradable products is widened.
Description
Technical field
The present invention relates to heat-resisting sheet material of a kind of biodegradation and preparation method thereof.
Background technology
Macromolecular material has used many decades, has brought huge change to people's life, has be unable to do without high score in lifeSub-material and goods thereof, but polymeric material and discarded object thereof want centuries to decompose, and it offers convenience to the mankindAlso brought serious " white pollution ", become one of Important Problems of global concern at present simultaneously. BiodegradationNational governments and people's attention is received in high molecular research and development, and is regarded as the strategic direction of following new material, alsoIt is the optimal path that solves white pollution. But the past for many years, biodegradation material is due to technical bottleneck and application limitSystem, is mainly used in the fields such as starch base, film class packaging and low temperature cold drink, and the research and development of sheet material aspect and application have often,But mainly exist fragility large taking polylactic acid modified as main sheet material and part calendered sheet, aging fast, heat-resisting difference and costThe problems such as height, prepare biodegradable heat-resisting sheet material by the tape casting and have no at present relevant successful Application.
Invention disclosed patent and defect thereof that technical scheme book related to the present invention is relevant are as follows:
Chinese patent (publication number CN101831086A) has proposed the modification sheet material of a kind of starch base and PVA, for tablewareDeng, but starch and the easy moisture absorption of glycerine used are unfavorable for preservation, security and service life are too short;
Chinese patent (publication number CN102352093A) proposes a kind of preparation method of Double-side delustered biodegradable sheet,In processing, product appearance and performance, have obvious progress, but that the blend of PLA and PBAT, calcium carbonate cannot solve is resistance toHeat problem, product still can only be applicable to low temperature environment;
Chinese patent (publication number CN102744850A) proposes a kind of method of double-colored biodegradation sheet material, but has only solvedThe processing problems of color aspect, does 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 goods, but the methodAdopt banburying, mode hot-forming and isothermal crystal to realize, cannot on ordinary tablet forming machine, prepare heat-resistant sheetMaterial, complex process, appropriate products narrow range;
Chinese patent (publication number CN1931907A) has proposed a kind of polylactic acid sheet material preparation method, but uses starch system,Aspect heat-resisting and hydrolysising aging, there is critical defect;
Chinese patent (publication number CN101362853A) has proposed the preparation method of the recyclable polylactic acid sheet material of a kind of low cost,The method provides the method for processing forming of good PLA base material sheet material, but the fragility of polylactic acid sheet material and heat labileProblem fails to solve, and is of limited application;
Chinese patent (publication number CN102977566A) has proposed the blend sheet material of a kind of PHA/PBS, at calendering technology andIn heat resistance, obtain remarkable breakthrough, but PHA exists, cost is high, smell large, be difficult to the problems such as industrialization, and calendering product existsThe aspect such as cost and application is difficult to commercialization;
Japan Patent (publication number 98122839.9) has proposed the preparation method of PBS/PLA/ filler blending and modifying, but mainBe applied to slide fastener and fastener products, and PLA cannot meet the requirement of strength of sheet material series products as decentralized photo;
Chinese patent (publication number CN102020773A) has proposed to prepare PLA-PBS copolymer by copolymerization mode, but all selectsWith oligomer, the fusing point of copolymer is low, poor heat resistance, the lifting that can not bring substantial properties of product;
Chinese patent (publication number CN102153846A) has proposed to prepare PHA/PETG composite sheet by rolling process, has solvedThe problems such as heat-resisting and processing, but cost is too high and cannot be used for the applications such as plastic uptake;
Chinese patent (publication number CN103540111A) discloses a kind of preparation method of polylactic acid sheet material of high-strength high-temperature resistant,No matter but the method is from theory or actual verification all shows intensity and heat-resisting disclosed numerical value, the dependence sound of all not reaching far awayBright toughening modifying and filling blend are to bring intensity and heat-resisting multiplication effect.
Summary of the invention
The research of biodegradation sheet material is a lot, but mostly only can serve as the application of simple non-returnable container aspect, as poly-The low temperature Blister product of lactic acid base material, PBS base material because too softly fail extensive use, produce and will serve as institutional packagingProduct cannot meet the requirement of mechanical property and heatproof completely. Along with the demand of people to biodegradation material, more and moreHigh-end goods biodegradation material has been proposed to the requirement of the aspects such as higher intensity, heat-resisting, durability, outward appearance.The heat-resisting sheet material of biodegradation with good mechanical property can meet the demand of part-structure external packing, and at goodsThe aspects such as cabinet transport, storage life, mechanical strength are broken through.
For this reason, the present invention is directed to defect and blank that prior art exists, comprehensive PLA and other biological degraded polyesterPerformance advantage, prepare one by composition and engineering and there is good mechanical property, weatherability and heat resistance, andAnd use common cast-sheet equipment processing, on cost, have more advantage.
The heat-resisting sheet material of a kind of biodegradation, by weight percentage, comprises following component: PLA 20%-50%; PBS35%-55%; Polyester 0%-10%; Nucleation reinforcing agent 1%-25%; Auxiliary agent 0.5%-5%, anti-UV agent 0%-0.5%.
Preferably, the middle heavy polymer that described PLA adopts molecular weight to be greater than 100,000, its polymerization is thirdLactide ring-opening polymerisation, low-molecular-weight lactic acid chain-extension polymerization, the one in the compound vertical ditch body of Pfansteihl or D-ALPHA-Hydroxypropionic acid; ItsIn, lactic acid has L (left-handed type) and D (dextroform), is generally L-type PLA, and both are compound can improve lactic acidDegree of crystallinity and fusing point.
Preferably, described PBS adopts succinic acid-butanediol ester condensation polymer, and molecular weight is greater than 100,000, carboxyl acid number contentLower than 20mg/mol; Described polyester adopts at least one in PBAT, PBSA, PHBV and P3HB4HB; Described nucleationReinforcing agent adopts one or more in talcum powder, kaolin, imvite, mica, wollastonite.
Preferably, described PBAT, PBSA are that yield strength is at least 7Mpa, and elongation at break is at least 500%, meltingIndex is 5-20g/10min, and terminal carboxyl group acid number content is lower than 20mg/mol; Described P3HB4HB is 4HB content3%-9%, described PHBV is that HV content is 3-10%, the melt index of described PBAT kind polyester is 5-20g/min.
Preferably, described antioxidant be four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester,2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl)-4 aminomethyl phenyl acrylate, tricresyl phosphite (2,4-di-t-butylbenzene) one or more in ester; Described lubricant adopt stearic acid, calcium stearate, zinc stearate,Dolomol, barium stearate, EBS, PE wax, TAF, erucyl amide, oleamide, titanate coupling agent and titanium aluminiumOne or more in acid esters composite coupler;
Described compatilizer adopt maleic anhydride class graft polymers, esters of acrylic acid, GMA class,One or several in peroxide and BASF chain extender;
Described hydrolysis-resisting agent adopts carbonization imines;
By gross weight ratio, described auxiliary agent comprises antioxidant 0.1%-0.25%, lubricant 0.1%-1.5%, compatilizer 0%-3%With hydrolysis-resisting agent 0.1%-1.2%.
The present invention's PLA used is Biodegradable Materials, comes from plant, after use, can under composting conditions, give birth toThing is degraded into water and carbon dioxide; There is good physical mechanics intensity (hot strength 60MPa), can be widely used in and blowThe application such as film, sheet material, fiber, injection moulding, but PLA exist fragility large (impact strength≤2j/m, percentage elongation≤5%,Poor heat resistance (vitrification point 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 are oldVoltinism is poor, has seriously restricted the application of PLA; Modification patent about PLA is a lot, but heat-resistingResearch in sheet applications is more rare.
The present invention's PBS material used is poly butylene succinate, is that in biodegradation material, combination property is comparatively outstandingKind, tensile yield strength is in 40MPa left and right, suitable with PP, ABS etc., and heat resistance is good, and HDT temperature approaches90 DEG C, after modification, serviceability temperature approaches 100 DEG C, has better heat resistance than other biological degradable material. ProcessabilityCan be very good, can on existing plastic processing common apparatus, carry out all kinds of processing and forming, be that current degradative plastics addsWork performance is best, and can with various filler blend, PBS can be with raw after existing general purpose polyester scrap build in additionProduce, cost is cheaper, and PBS only just degrades under the specified microorganisms such as compost, water body condition,Normal storage and use procedure performance are stable. The shortcoming of PBS is its degree of crystallinity high (30%-60%), and physical property is partially crisp.
The other biological degraded polyester material that the present invention uses has also comprised PBAT (poly-succinic-terephthalic acid (TPA)-butanediolEster), PBSA (poly-succinic-adipic acid-butanediol ester), PHA (PHB and copolymer thereof) etc., theseAlso be to there is biodegradation character, for the lifting of modified product combination property provides larger selection, be conducive to heat-resistingThe application variation of sheet material.
The present invention also provides a kind of method of preparing the heat-resisting sheet material of biodegradation, comprises following step:
Steps A: predrying: adopt dehumidifying device that PLA and polyester are dried in advance, moisture is reduced toIn 150ppm;
Step B: mix: PLA, PBS and polyester are put into airtight homogenizer and mix, temperature is 20 DEG C-50 DEG C, time 5-15min, puts into the first weight-loss metering device stand-by after mixing; Nucleation reinforcing agent and auxiliary agent are put into closeClose high-speed mixer and fully mix, temperature 20-40 DEG C, time 10-20Min, puts into the second weight-loss metering device and treats after mixingWith;
Step C: mixing plasticizing, according to proportioning, regulates weightless feeder parameter, respectively by major ingredient, powder in proportion simultaneouslyJoin melt blending in parallel dual-screw extruding machine, melting temperature is 120 DEG C-180 DEG C, screw speed 100-400rpm;
Step D: granulation: by the blend through double screw extruder plasticizing by the mode granulation of water cooling tie rod pelletizing orPerson is prepared into evengranular particle by the mode of flour milling pelletizing under water;
Step e: dry again: the heat resistance modified resin of biodegradation that uses dehumidifying device that step D is obtained is dry again,Moisture is reduced in 150ppm;
Step F: sheet forming: the dried resin that step e is obtained adds in sheet extruder, at 130-210 DEG CLower extrusion sheet,, sizing cooling by three rollers, obtains heat-resisting sheet material after adjustment dimensions.
Wherein, the mode of water cooling tie rod pelletizing refers to from extruder pull-out material strip and after cooling hardening, dries up tank againAnd enter pelleter pelletizing, and the mode of flour milling pelletizing is under water also the technique of granulation, cutting knife and porous dies laminating, and cutting knife revolvesTurn material out of extruder is cut off after again with water cooling laggard enter centrifuge drying.
Preferably, in step C, temperature is 120 DEG C-165 DEG C, and screw speed is 180-350rpm.
The present invention also provides a kind of twin-screw mixer extrusion system for the preparation of heat-resisting sheet material, comprises setting graduallyHigh-speed mixer, conveyer, weight-loss metering device, powder weight-loss metering device, exhaust outlet, double-screw mixing for resinUnit, bosh, hair dryer, pelleter and storage tank are extruded in refining, twin-screw mixer screw slenderness ratio is not less than 40:1, mixing gear block is not less than 7 groups.
Preferably, twin-screw mixer screw slenderness ratio 44:1 or 42:1, mixing gear block is 10 groups or 13 groups.
The present invention also provides a kind of forming processing system for the preparation of heat-resisting sheet material, comprises the drying cartridge setting graduallyPut, drawing-in device, fusion plastification extrusion device, three-roll press-polishing cooling and shaping device, traction cutting means and wrap-up.
The invention has the beneficial effects as follows: the invention provides the common casting technique of a kind of use and prepare the heat-resisting sheet material of biodegradationMethod, solve that current polylactic acid sheet material fragility is large, thermo-labile and calendered sheet cost is high, the narrow grade of range of application is askedTopic, realizes low cost, high efficiency production has good physical and mechanical property, processability and stable on heating biodegradation sheetMaterial, is widely used in the fields such as electronic product, cosmetics, disposable heat-resisting articles for use, widens answering of biodegradation goodsUse scope.
Brief description of the drawings
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 of the present invention for the preparation of heat-resisting sheet material.
Detailed description of the invention
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
As shown in Figure 1, a kind of twin-screw mixer extrusion system for the preparation of heat-resisting sheet material, comprises the height setting graduallySpeed mixer 1, conveyer 2, weight-loss metering device 3, powder weight-loss metering device 4, exhaust outlet 5, two for resinScrew mixing is extruded unit 6, bosh 7, hair dryer 8, pelleter 9 and storage tank 10.
As shown in Figure 2, a kind of forming processing system for the preparation of heat-resisting sheet material, comprise the drying device 11 that sets gradually,Drawing-in device 12, fusion plastification extrusion device 13, three-roll press-polishing cooling and shaping device 14, traction cutting means 15 and rollingDevice 16.
Embodiment 1
By weight percentage, by 8000 order talcum powder 3%, titanium dioxide 2%, PE wax 0.75%, calcium stearate 0.5%, barThis husband's chain extender 0.5%, 10100.1%, carbonization imines 1.15% is put after adding 40 DEG C of mixing 20min of homogenizerPut in B weight-loss metering device for subsequent use, by the P3HB4HB10% of 4HB content 6%, PBS37%, PLA 45% dehumidifiesAfter dry, add after mixing 15min under homogenizer normal temperature and place A weight-loss metering device, with B compound withTime enter double screw extruder melt blending, water stretching and granulation, can be used for preparing various sheet materials and other various goods.By joining after above-mentioned resin drying in the sheet extruder that screw diameter is 130mm, at 160-195 DEG C of extrusion temperature,Under 40rpm extruded velocity, prepare 1.0-1.8mm thick sheet, there is good outward appearance and good combination property.
Embodiment 2
By weight percentage, by 10000 order talcum powder 8%, 6000 order micas 3%, EBS0.5%, zinc stearate 0.5%,Titanate coupling agent 0.2%, 10100.1%, phosphite ester kind antioxidant 0.1%, UV5270.3%, carbonization imines 0.3%,Add 50 DEG C of homogenizers to mix to place in B weight-loss metering device after 20min for subsequent use, by HV content 10%PHBV5%, PBS40%, PLA 40%, PBAT2% adds after mixing 10min under homogenizer normal temperature and placesA weight-loss metering device enters double screw extruder melt blending with B compound simultaneously, and water cooling bracing granulation is availableIn the various sheet materials of preparation and other various goods. The sheet material that screw diameter is 130mm will be joined after above-mentioned resin dryingIn extruder, at 160-185 DEG C of extrusion temperature, under 30rpm extruded velocity, prepare 0.5-1.65mm thick sheet, toolThere are good outward appearance and good combination property.
Embodiment 3
By weight percentage, by 3000 order wollastonites 5%, nano imvite 1%, 5000 order kaolin 4%, TAF0.5%,Stearic acid 0.5%, titanium Aluminate composite coupler 0.1%, 10760.1%, tricresyl phosphite (2,4-di-t-butylbenzene)Ester 0.1%, maleic anhydride 0.2%, cumyl peroxide 0.1%, carbonization imines 0.4%, adds 50 DEG C of homogenizersMixing 30min places in B weight-loss metering device for subsequent use afterwards, by PBSA5%, and PBS38%, PLA 45% is dryAfter add after mixing 8min under homogenizer normal temperature and place A weight-loss metering device, enter with B compound simultaneouslyDouble screw extruder melt blending, stretching and granulation, can be used for preparing various sheet materials and other various goods. By above-mentioned treeAfter fat is dry, join in the sheet extruder that screw diameter is 130mm, at 160-190 DEG C of extrusion temperature, 20-35rpmUnder extruded velocity, prepare 0.3-1.2mm thick sheet, there is good outward appearance and good combination property.
Performance is as shown in table 1, and wherein comparative example modification PLA, modification PBS, hard PVC and HIPS purchase in market.
Table 1
By known to table 1, the prepared heat-resisting sheet material of the present invention possesses following performance:
1. have good comprehensive strength, the packaging intensity that can meet the hard sheets such as most of PS, PVC, PETG is wantedAsk, and kept good toughness;
2. there is good heat resistance, can meet packaging structure part to heat-resisting requirement;
3. extended weatherability, especially hydrothermal aging, has extended the shelf life of biodegradation sheet material greatly;
4. good melt strength, has ensured the possibility of the biodegradation sheet material of the above thickness of moulding 1.6mm, widensThe application of biodegradation sheet material;
5. use twin-screw mixer and ordinary tablet forming machine to produce to have that output is large, cost is low, promote the advantages such as fast.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assertSpecific embodiment of the invention is confined to these explanations. For general technical staff of the technical field of the invention,Without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to thisThe protection domain of invention.
Claims (10)
1. the heat-resisting sheet material of biodegradation, is characterized in that, by weight percentage, comprises following component: PLA 20%-50%; PBS35%-55%; Polyester 0%-10%; Nucleation reinforcing agent 1%-25%; Auxiliary agent 0.5%-5%, anti-UV agent 0%-0.5%.
2. the heat-resisting sheet material of biodegradation as claimed in claim 1, it is characterized in that, the middle heavy polymer that described PLA adopts molecular weight to be greater than 100,000, its polymerization is lactide ring-opening polymerisation, low-molecular-weight lactic acid chain-extension polymerization, the one in the compound vertical ditch body of Pfansteihl or D-ALPHA-Hydroxypropionic acid;
Described PBS adopts succinic acid-butanediol ester condensation polymer, and molecular weight is greater than 100,000, and carboxyl acid number content is lower than 20mg/mol;
Described polyester adopts at least one in PBAT, PBSA, PHBV and P3HB4HB;
Described nucleation reinforcing agent adopts one or more in talcum powder, kaolin, imvite, mica, wollastonite and titanium dioxide;
Described auxiliary agent comprises antioxidant, lubricant, compatilizer and hydrolysis-resisting agent;
Described anti-UV agent adopts UV527.
3. the heat-resisting sheet material of biodegradation as claimed in claim 2, is characterized in that, described PBAT, PBSA are that yield strength is at least 7Mpa, and elongation at break is at least 500%, and melt index is 5-20g/10min, and terminal carboxyl group acid number content is lower than 20mg/mol; Described P3HB4HB is 4HB content 3%--9%, and described PHBV is that HV content is 3-10%, and the melt index of described PBAT kind polyester is 5-20g/min.
4. the heat-resisting sheet material of biodegradation as claimed in claim 2, it is characterized in that, described antioxidant is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl-5 methyl-benzyl) one or more in-4 aminomethyl phenyl acrylate, tricresyl phosphite (2,4-di-t-butylbenzene) ester;
Described lubricant adopts one or more in stearic acid, calcium stearate, zinc stearate, dolomol, barium stearate, EBS, PE wax, TAF, erucyl amide, oleamide, titanate coupling agent and titanium Aluminate composite coupler;
Described compatilizer adopts one or several in maleic anhydride class graft polymers, esters of acrylic acid, GMA class, peroxide, maleic anhydride and BASF chain extender;
Described hydrolysis-resisting agent adopts carbonization imines;
By gross weight ratio, described auxiliary agent comprises antioxidant 0.1%-0.25%, lubricant 0.1%-1.5%, compatilizer 0%-3% and hydrolysis-resisting agent 0.1%-1.2%.
5. prepare the heat-resisting sheet material of biodegradation as claimed in claim 1, it is characterized in that, comprise following step:
Steps A: predrying: adopt dehumidifying device that PLA and polyester are dried in advance, moisture is reduced in 150ppm;
Step B: mix: PLA, PBS and polyester are put into airtight homogenizer and mix, temperature is 20 DEG C-50 DEG C, and time 5-15min, puts into the first weight-loss metering device stand-by after mixing; Nucleation reinforcing agent and auxiliary agent are put into airtight high-speed mixer and fully mix, temperature 20-40 DEG C, time 10-20Min, puts into the second weight-loss metering device stand-by after mixing;
Step C: mixing plasticizing, according to proportioning, regulates weightless feeder parameter, respectively raw material is joined to melt blending in Co rotating Twin Screw Extrusion system in proportion simultaneously, melting temperature is 120 DEG C-180 DEG C, screw speed 100-400rpm;
Step D: granulation: will be prepared into evengranular particle by the mode granulation of water cooling tie rod pelletizing or by the mode of flour milling pelletizing under water through the blend of twin-screw extrusion system plasticizing;
Step e: dry again: use the heat resistance modified resin of biodegradation that dehumidifying device obtains step D to go and be dried again, moisture is reduced in 150ppm;
Step F: sheet forming: the dried resin that step e is obtained adds in forming processing system, extrusion sheet at 130-210 DEG C,, sizing cooling by three rollers, obtains heat-resisting sheet material after adjustment dimensions.
6. method as claimed in claim 5, is characterized in that, in step C, temperature is 120 DEG C-165 DEG C, and screw speed is 180-350rpm.
7. the twin-screw mixer extrusion system for the preparation of heat-resisting sheet material as claimed in claim 1; it is characterized in that; comprise that the high-speed mixer, conveyer, resin weight-loss metering device, powder weight-loss metering device, exhaust outlet, the twin-screw mixer that set gradually are extruded unit, bosh, hair dryer, pelleter and storage tank, twin-screw mixer screw slenderness ratio is not less than 40:1, mixing gear block is not less than 7 groups.
8. the forming processing system for the preparation of heat-resisting sheet material as claimed in claim 1, it is characterized in that, comprise the drying device, drawing-in device, fusion plastification extrusion device, three-roll press-polishing cooling and shaping device, traction cutting means and the wrap-up that set gradually.
9. twin-screw mixer extrusion system as claimed in claim 7, is characterized in that, twin-screw mixer screw slenderness ratio is 44:1 or 42:1, and mixing gear block is 10 groups or 13 groups.
10. the application of the heat-resisting sheet material of biodegradation as claimed in claim 1.
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