CN114702799A - Biodegradable polylactic acid plastic uptake sheet - Google Patents
Biodegradable polylactic acid plastic uptake sheet Download PDFInfo
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- CN114702799A CN114702799A CN202210225742.9A CN202210225742A CN114702799A CN 114702799 A CN114702799 A CN 114702799A CN 202210225742 A CN202210225742 A CN 202210225742A CN 114702799 A CN114702799 A CN 114702799A
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- polylactic acid
- biodegradable polylactic
- pbat
- plla
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 46
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 45
- 229920003023 plastic Polymers 0.000 title claims abstract description 28
- 239000004033 plastic Substances 0.000 title claims abstract description 28
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 42
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 39
- 239000002667 nucleating agent Substances 0.000 claims abstract description 35
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229920001896 polybutyrate Polymers 0.000 claims abstract 4
- 235000012424 soybean oil Nutrition 0.000 claims description 17
- 239000003549 soybean oil Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 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
- 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
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 20
- 238000002425 crystallisation Methods 0.000 abstract description 13
- 230000008025 crystallization Effects 0.000 abstract description 13
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 27
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- PFQAIMSYOXGWGG-UHFFFAOYSA-N N'-benzoylbenzohydrazide decanedioic acid Chemical compound C(C1=CC=CC=C1)(=O)NNC(C1=CC=CC=C1)=O.C(=O)(O)CCCCCCCCC(=O)O PFQAIMSYOXGWGG-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of polylactic acid materials, and provides a biodegradable polylactic acid plastic uptake sheet which comprises the following components in parts by weight: the composite material comprises, by weight, 50-95 parts of PLLA, 3-35 parts of PBAT, 3-10 parts of a compatilizer, 2-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler. In the invention, the dosage of PBAT is strictly controlled, PLLA is selected as a raw material, and quasi-orthorhombic crystals and orthorhombic crystals can be generated during crystallization; the nucleating agent can promote quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA to be further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and the obtained sheet has more stable performance due to a unique crystallization mode.
Description
Technical Field
The invention relates to the technical field of polylactic acid materials, in particular to a biodegradable polylactic acid plastic uptake sheet.
Background
The development of biodegradable materials is increasing day by day, the application range is expanding continuously, and the biodegradable materials are gradually replacing the traditional plastics in the fields of tableware, disposable packages, disposable lunch boxes and daily necessities. The fully biodegradable material can be completely decomposed into water, carbon dioxide and organic matter components in natural environment or composting condition, and has no negative influence on environment, so that the fully biodegradable material has great development and application in the aspects of commodity packaging, express bags, heat shrinkable films, adhesive tapes, agricultural mulching films, disposable knife and fork spoons, disposable lunch boxes, straws, plastic uptake and the like in recent years.
In the prior art, polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT) are common raw materials for preparing biodegradable materials. Wherein PLA has high rigidity and crystallinity; the PBAT has the characteristics of both poly (adipate-co-terephthalate) and polybutylene terephthalate (PBT), has good ductility and elongation at break, good heat resistance and impact resistance, and good biodegradability of the PLA and the PBAT.
In order to avoid the material from being broken in the cutting process and easy to be cut and formed, in the prior art, the ductility and the elongation at break of the material are often improved by increasing the dosage of PBAT, so that the notch impact performance of the sheet is improved. Although the notch impact performance of the material obtained by the scheme can be effectively improved, the high temperature resistance of the material, namely the Vicat temperature, is obviously reduced (lower than 50 ℃), so that the requirement of the biodegradable material on the high temperature performance cannot be better met.
Disclosure of Invention
The invention aims to provide a biodegradable polylactic acid plastic uptake sheet which has excellent notch impact performance and high temperature resistance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a biodegradable polylactic acid plastic uptake sheet which comprises the following components in parts by weight: the composite material comprises, by weight, 50-95 parts of PLLA, 3-35 parts of PBAT, 3-10 parts of a compatilizer, 2-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler;
the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent;
the compatilizer is at least one of PBAT-g-GMA, PBAT-g-MHA and PBST-g-GMA;
the preparation method of the biodegradable polylactic acid plastic suction sheet comprises the steps of granulating, drying, extruding and forming and annealing in sequence; the extrusion forming device is a single-screw extruder, and the temperature of each part of the single-screw extruder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 200 ℃, the fourth zone is 210 ℃ and the head is 200 ℃.
Preferably, the annealing temperature is 150-160 ℃, and the annealing time is 20-40 s.
Preferably, the weight average molecular weight of the PLLA is 30000-3000000, and the molecular weight distribution is 1.5-5.
Preferably, the weight average molecular weight of the PBAT is 20000-130000, and the molecular weight distribution is 1.5-4.
Preferably, the dispersant comprises at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax and polyethylene wax.
Preferably, the plasticizer includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride.
Preferably, the coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum titanate coupling agent.
Preferably, the chain extender includes a polyurethane chain extender and/or an epoxy chain extender.
Preferably, the polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
Preferably, the filler comprises at least one of calcium carbonate, montmorillonite and talc.
The invention provides a biodegradable polylactic acid blister sheet, which is prepared by strictly controlling the dosage of PBAT, selecting poly-L-lactic acid as a raw material, and generating quasi-orthorhombic crystals and orthorhombic crystals when PLLA is crystallized in the extrusion forming process; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and a unique crystallization mode enables the sheet to have more stable performance, so that the notch impact performance and the high temperature resistance of the sheet are improved; meanwhile, the compatilizer is added into the raw materials, so that the compatibility among the raw materials is promoted, and the stability of the sheet is further improved; and finally, the temperature of each part of the double-screw extruder is strictly controlled, so that the optimal performance of the sheet is realized. Experimental results show that the biodegradable polylactic acid plastic uptake sheet obtained by the technical scheme provided by the invention has the notch impact performance not lower than 5.4KJ/m2The high temperature resistance is not lower than 70 ℃.
Detailed Description
The invention provides a biodegradable polylactic acid plastic uptake sheet which comprises the following components in parts by weight: the composite material comprises, by weight, 50-95 parts of PLLA, 3-35 parts of PBAT, 3-10 parts of a compatilizer, 2-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler.
The biodegradable polylactic acid plastic uptake sheet comprises, by weight, PLLA 50-95 parts, preferably 55-85 parts. In the present invention, the PLLA represents poly-l-lactic acid. In the extrusion forming process, PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, and the complex forms triangular crystal nuclei at the initial stage of crystallization and has a unique crystallization mode, so that the sheet performance is more stable.
In the invention, the weight average molecular weight of the PLLA is preferably 30000-3000000, more preferably 100000-2000000; the molecular weight distribution is preferably 1.5 to 5, more preferably 2.5 to 3.5. The weight average molecular weight of the PLLA is controlled in the range, so that the phenomenon that the molecular weight is too small, the flowability of the sheet is changed greatly in the processing process, and the toughness of the sheet is influenced is avoided; the molecular weight is too high, and the sheet material is difficult to melt; and the PLLA within the molecular weight range is proper in price, so that the cost of the sheet is reduced. By controlling the molecular weight distribution in the above range, the PLLA performance is stable.
The source of the PLLA is not particularly specified in the present invention, and conventional commercially available products well known to those skilled in the art may be used. In the embodiment of the invention, the PLLA is a PLLA of L175 type. In an actual production plant, L in the L175 represents high optical rotation. In the comparison of the present invention, LX175 is selected as the PLLA. In an actual production factory, LX in the LX175 represents low optical rotation.
The biodegradable polylactic acid plastic uptake sheet comprises 3-35 parts of PBAT and preferably 5-30 parts of PLLA by weight of 50-95 parts of PBAT. In the present invention, the PBAT represents a copolymer of butylene adipate (PBA) and butylene terephthalate (PBT). In the present invention, the PBAT has not only good ductility and elongation at break, but also good heat resistance and impact properties, and in addition, has excellent biodegradability, and exists as a base material for biodegradable sheets.
In the invention, the weight average molecular weight of PBAT is preferably 20000-130000, more preferably 60000-95000; the molecular weight distribution is preferably 1.5 to 4, more preferably 2.5 to 3.5. The weight average molecular weight of the PBAT is controlled in the range, so that the conditions that the molecular weight is too small, the mobility of the sheet is changed greatly in the processing process and the toughness of the sheet is influenced are avoided; the molecular weight is too high, and the sheet material is difficult to melt; meanwhile, the PBAT with the molecular weight is proper in price, and the cost of the sheet is favorably reduced. The molecular weight distribution of the PBAT is controlled in the range, so that the PBAT has stable performance.
The source of the PBAT is not specified in the present invention, and conventional commercial products well known to those skilled in the art may be used. In the embodiment of the invention, the PBAT is selected from conventional commercial products with the brand number TH 801T.
The biodegradable polylactic acid plastic uptake sheet comprises, by weight, 50-95 parts of PLLA, 3-10 parts of a compatilizer, and preferably 5-8 parts of the compatilizer. In the invention, the compatilizer can promote the compatibility among raw materials, thereby improving the notch impact performance of the sheet.
In the present invention, the compatibilizer is at least one of PBAT-g-GMA, PBAT-g-MHA, and PBST-g-GMA, preferably PBST-g-GMA. In the present invention, the PBAT-g-GMA represents poly (butylene adipate/terephthalate) grafted glycidyl methacrylate; PBAT-g-MHA represents poly (butylene adipate terephthalate) -grafted maleic anhydride; PBST-g-GMA stands for polybutylene succinate-butylene terephthalate grafted glycidyl methacrylate. In the invention, the PBST-g-GMA graft has the advantages of high grafting efficiency, short polymer synthesis time and the like, and is relatively low in price.
The source of the compatibilizer is not particularly specified in the invention, and the compatibilizer can be prepared by a preparation method well known to a person skilled in the art or a commercially available product can be directly purchased.
The biodegradable polylactic acid plastic uptake sheet comprises, by weight, 50-95 parts of PLLA, 2-20 parts of a nucleating agent, preferably 3-5 parts of the nucleating agent. In the invention, the nucleating agent can promote quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA to be further subjected to stereocomplex, so that a more stable crystal structure and a stereocomplex are generated, triangular crystal nuclei are formed in the complex at the early stage of crystallization, and the sheet performance is more stable due to a unique crystallization mode.
In the invention, the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent. In the invention, the D070 nucleating agent represents dextrorotatory polylactic acid; TMC-300 represents dibenzoylhydrazide sebacate; CZ-500 represents polyhydrazide imine compounds. In the invention, the nucleating agent can promote quasi-orthorhombic crystals formed by PLLA and the nucleating agent when orthorhombic crystals are further subjected to stereo-composition, and the obtained sheet has better comprehensive performance.
The source of the nucleating agent is not particularly specified in the present invention, and commercially available products known to those skilled in the art can be used.
The biodegradable polylactic acid plastic uptake sheet provided by the invention comprises, by weight of PLLA 50-95 parts, 0.01-5 parts of a dispersing agent, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the present invention, the dispersant can uniformly disperse inorganic and organic solid and liquid particles which are difficult to dissolve in liquid, and can prevent the particles from settling and coagulating to form a stable suspension.
In the present invention, the dispersant preferably includes at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax and polyethylene wax, preferably ethylene bis stearamide, i.e., EBS. In the invention, the ethylene bis stearamide has low odor and low addition content, has the function of internal and external lubrication, and can be used as the dispersant to obtain a sheet with good comprehensive performance.
The source of the dispersant is not particularly specified in the present invention, and the dispersant can be prepared by a preparation method well known to those skilled in the art or a commercially available product can be directly purchased.
The biodegradable polylactic acid plastic uptake sheet provided by the invention comprises, by weight of PLLA 50-95 parts, 0.01-5 parts of a plasticizer, preferably 0.1-3 parts, and more preferably 0.5-1 part. In the invention, the plasticizer can reduce intermolecular force, so that the viscosity of the polymer is reduced, and the flexibility is enhanced.
In the present invention, the plasticizer preferably includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride, and more preferably epoxidized soybean oil. In the invention, the epoxy group of the epoxidized soybean oil has reactivity with the group resin PLLA, so that the comprehensive performance of the obtained sheet can be further improved.
The source of the plasticizer is not particularly limited in the present invention, and a commercially available product well known to those skilled in the art may be used.
The biodegradable polylactic acid plastic uptake sheet provided by the invention comprises, by weight of PLLA 50-95 parts, 1-95 parts of filler, preferably 5-50 parts, and more preferably 10-25 parts. In the present invention, the filler may enhance the overall performance of the polymer sheet.
In the present invention, the filler preferably includes at least one of calcium carbonate, montmorillonite and talc. In the present invention, the particle diameter D50 of the filler is preferably 1.2 to 3 μm, and more preferably 1.5 to 2.5 μm. The particle size of the filler is controlled within the range, so that the dispersion uniformity of the filler in the raw materials can be improved, and the mechanical property of the sheet is further improved; meanwhile, the increase of the production cost caused by the over-small particle size is avoided, so that the raw material cost for producing the sheet is reduced.
The source of the filler is not specifically defined in the present invention, and a commercially available product well known to those skilled in the art may be used.
The biodegradable polylactic acid plastic uptake sheet comprises, by weight of 50-95 parts of PLLA, 0.01-5 parts of coupling agent, preferably 0.03-0.1 part. In the invention, the coupling agent can realize the effect of modifying the filler, thereby improving the dispersibility of the filler in the raw materials.
In the present invention, the coupling agent preferably includes at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum-titanium ester coupling agent, and more preferably an aluminum-titanium ester coupling agent. The aluminum-titanium ester coupling agent is used as the coupling agent of the invention, so that the aluminum-titanium ester coupling agent can be more easily and uniformly dispersed in a raw material system.
The source of the coupling agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The biodegradable polylactic acid plastic uptake sheet provided by the invention comprises, by weight of PLLA 50-95 parts, 0.01-5 parts of chain extender, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the invention, the chain extender can react with the polymer in the raw material, so that the molecular weight of the polymer is improved, and the mechanical property of the sheet is further improved.
In the present invention, the chain extender preferably includes a polyurethane chain extender and/or an epoxy chain extender, and the polyurethane chain extender preferably includes ADR4375 and/or ADR 4400; the epoxy chain extender preferably includes CE1105 and/or 3525G. The chain extender is selected as the chain extender of the technical scheme of the invention, so that the polymer with proper polymerization degree can be more easily obtained, and the optimal comprehensive performance of the material can be realized due to the proper polymerization degree of the obtained polymer material.
The source of the chain extender is not particularly specified in the present invention, and commercially available products well known to those skilled in the art may be used.
The preparation method of the biodegradable polylactic acid plastic uptake sheet comprises the steps of granulation, drying, extrusion forming and annealing which are sequentially carried out.
In the present invention, the method for preparing the biodegradable polylactic acid blister sheet preferably comprises: and mixing the PLLA, the PBAT, the compatilizer, the coupling agent, the nucleating agent, the chain extender, the dispersant, the filler and the plasticizer, and then sequentially granulating, drying, extruding and molding and annealing to obtain the biodegradable polylactic acid plastic-absorbing sheet.
In the present invention, the PLLA, PBAT, compatibilizer, nucleating agent and filler are preferably dried before mixing. The drying method is not particularly limited in the present invention, and the moisture in the raw materials may be removed by a drying method known to those skilled in the art. The invention dries the raw materials in advance, can avoid the influence of moisture in the raw materials on the granulation process, and thus reduces the performance of the sheet.
The invention preferably mixes the coupling agent and the filler to obtain the activated filler, mixes the activated filler with PLLA, PBAT, the compatilizer, the nucleating agent, the chain extender, the dispersant and the plasticizer, and then carries out granulation. The invention is beneficial to improving the dispersibility of the filler in the formula by activating the filler by using the coupling agent in advance.
In the present invention, the apparatus for granulation is preferably a twin-screw extruder. The granulation mode is not specially specified in the invention, and the granules can be obtained by adopting a granulation mode known by a person skilled in the art and utilizing a double-screw extruder for granulation. The raw materials are granulated, so that the dispersibility among the raw materials is improved in the later extrusion forming process, and the comprehensive performance of the sheet is improved.
In the present invention, the temperature of each part of the twin-screw extruder is preferably: first zone 150 deg.C, second zone 160 deg.C, third zone 160 deg.C, fourth zone 170 deg.C, fifth zone 170 deg.C, sixth zone 175 deg.C, seventh zone 175 deg.C, eighth zone 170 deg.C, ninth zone 165 deg.C, tenth zone 165 deg.C, eleventh zone 165 deg.C, twelfth zone 165 deg.C, head 180 deg.C; the screw rotating speed of the double-screw extruder is preferably 60-600 rpm, more preferably 100-500 rpm, and most preferably 200-400 rpm; the length-diameter ratio L/D of the screw of the double-screw extruder is preferably (40-72): 1, and more preferably 48: 1. The invention limits all process parameters of the double-screw extruder in the above range, and the obtained sheet has good comprehensive performance.
The drying method after granulation is not particularly specified in the present invention, and the granules prepared after granulation are dried by a drying method well known to those skilled in the art, and the moisture in the granules during granulation is removed.
In the invention, the extrusion forming device is a single-screw extruder. The extrusion molding operation is not specially specified in the invention, and the sheet can be prepared by adopting the extrusion molding operation known by the technical personnel in the field and utilizing a single-screw extruder.
In the invention, the temperature of each part of the single-screw extruder is preferably 180 ℃ in the first zone, 190 ℃ in the second zone, 200 ℃ in the third zone, 210 ℃ in the fourth zone and 200 ℃ in a machine head; the screw rotating speed of the single-screw extruder is preferably 100-400 rpm, and more preferably 150-300 rpm; the length-diameter ratio L/D of the screw of the single-screw extruder is preferably 40-60: 1, and more preferably 52: 1; the roll tablets of the single screw extruder are preferably one-roll, two-roll and three-roll tablets. In the present invention, the temperature of the one roll is preferably 25 ℃, the temperature of the two rolls is preferably 38 ℃, and the temperature of the three rolls is preferably 50 ℃. The invention is not particularly limited as to the manner of rolling, and sheets may be prepared by horizontal rolling, oblique rolling or vertical rolling, which are well known to those skilled in the art. The invention limits the technological parameters of each part of the single screw extruder in the range, and the obtained sheet has better comprehensive performance.
In the invention, the annealing temperature is preferably 140-170 ℃, and more preferably 150-160 ℃; the annealing time is preferably 20-40 s, and more preferably 30 s. According to the invention, the sheet crystallization is promoted through annealing treatment, so that the heat resistance of the sheet is improved.
The invention provides a biodegradable polylactic acid blister sheet, which is prepared by strictly controlling the dosage of PBAT, selecting poly-L-lactic acid as a raw material, and generating quasi-orthorhombic crystals and orthorhombic crystals when PLLA is crystallized in the extrusion forming process; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and a unique crystallization mode enables the sheet to have more stable performance, so that the notch impact performance and the high temperature resistance of the sheet are improved; meanwhile, the compatilizer is added into the raw materials, so that the compatibility among the raw materials is promoted, and the stability of the sheet is further improved; and finally, the temperature of each part of the double-screw extruder is strictly controlled, so that the optimal performance of the sheet is realized.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the specific specification or abbreviation of the raw materials is as follows: PLLA (designation L175, weight average molecular weight 207000g/mol, molecular weight distribution 1.8), PBAT (designation TH801T, weight average molecular weight 88000, molecular weight distribution 2.2), compatibilizer: PBAT-g-GMA (trade name BP-02), filler: nano calcium carbonate (trade name XF-10, particle diameter D)501.2 μm) or talc (trade name HTP05L, particle sizeD501.2 μm), coupling agent: aluminum-titanium coupling agent, nucleating agent: d-polylactic acid D070 or sebacic acid dibenzoylhydrazine TMC-300, and a plasticizer: epoxidized soybean oil chain extender: ADR-4400, dispersant: ethylene bis stearamide, abbreviated as EBS.
Example 1
The components and the dosage are as follows: 85 parts of L175, 5 parts of TH801T, 5 parts of PBAT-g-GMA, 0.8 part of epoxidized soybean oil, 3 parts of D070, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Pretreatment: (1) drying D070, L170, TH801T and PBAT-g-GMA in a blast oven at 80 ℃ for 4 h; HTP05L and XF-10 were dried in a 105 ℃ forced air oven for 4 h.
(2) 99 parts of talc and 1 part of an aluminum-titanium coupling agent were stirred at 90 ℃ for 5 minutes to obtain activated HTP 05L.
The preparation method comprises the following specific steps:
(I) respectively sucking the L175, the TH801T and the PBAT-g-GMA in parts by weight into a temporary storage bin under negative pressure, injecting epoxidized soybean oil into the temporary storage bin from a liquid peristaltic pump in three zones, uniformly mixing the D070, the ADR-4400 and the EBS by using a vertical high-speed mixer, then feeding the mixture into a small material temporary storage bin, and activating HTP05L in a powder temporary storage bin to finish the storage work of raw materials.
(II) adding the raw materials prepared in the step (I) into a double-screw extruder for extrusion and granulation to obtain granules; the temperature of each zone of the double-screw machine is as follows: first zone 150 deg.C, second zone 160 deg.C, third zone 160 deg.C, fourth zone 170 deg.C, fifth zone 170 deg.C, sixth zone 175 deg.C, seventh zone 175 deg.C, eighth zone 170 deg.C, ninth zone 165 deg.C, tenth zone 165 deg.C, eleventh zone 165 deg.C, twelfth zone 165 deg.C, head 180 deg.C; the rotating speed of the screw is 260rpm, and the length-diameter ratio L/D is 48/1;
(III) drying the granules obtained in the step (II) in a forced air oven at 80 ℃ for 4 hours to obtain dried granules;
(IV) adding the dried granules obtained in the step (III) into a single-screw extruder for extrusion to obtain the primary biodegradable polylactic acid plastic suction sheet. The temperature of each zone of the single screw machine is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 200 ℃, the fourth zone is 210 ℃ and the head is 200 ℃; the screw speed is preferably 230rpm, the screw length-diameter ratio L/D is 52:1, 3-roll sheeting is used, the first roll nip is as close to the die head as possible and slightly lower than the die head, air inclusion is prevented, and the three-roll temperature is set: one roll at 25 deg.C, two rolls at 38 deg.C, and three rolls at 50 deg.C.
(V) sequentially passing the primary biodegradable polylactic acid blister sheet obtained in the step (IV) through a heating device, a blister device and a cutting device under the traction of traction equipment to obtain a final biodegradable polylactic acid blister sheet; wherein the temperature of the heat treatment is 150 ℃ and the time is 30S.
Example 2
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 80 parts of L175, 10 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Example 3
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 75 parts of L175, 15 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Example 4
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 70 parts of L175, 20 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Example 5
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 65 parts of L175, 25 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Example 6
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 60 parts of L175, 30 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Comparative example 1
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 65 parts of L175, 25 parts of TH801T, 5 parts of PBAT-g-GMA, 1 part of nucleating agent D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Comparative example 2
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 65 parts of LX175, 25 parts of TH801T, 5 parts of PBAT-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
Comparative example 3
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 68 parts of L175, 25 parts of TH801T, 5 parts of PBAT-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS, 0.5 part of TMC-300 and 2 parts of activated HTP 05L.
Comparative example 4
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 68 parts of L175, 25 parts of TH801T, 1 part of PBAT-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 2 parts of activated HTP 05L.
The sheets prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance tests, and the test results are shown in Table 1.
And (4) testing standard: the notch impact is according to GB/T1843-2008, 1 type; tensile strength GB/T1040.2-2006, type 1A; bending strength GB/T9341-; the Vicat softening temperature is in accordance with GB/T1633-2000.
TABLE 1 results of Performance test of sheets prepared in examples 1 to 6 and comparative examples 1 to 4
The results in table 1 show that the compatilizer in the system can well improve the compatibility of PLA and PBAT, change the size and the dispersion degree of the dispersion phase in the system, the proportion of the D-type PLA in the system is improved, the higher the heat-resistant temperature of the plastic-absorbing material is, the TMC-300 can also improve the heat-resistant performance of the material, the effect is weaker than that of the D-type PLA, the notch impact strength of the material is gradually increased along with the increase of the PBAT content of the system, and the heat-resistant temperature is gradually reduced; when the PLA with low optical purity is used for preparing a high-toughness plastic-absorbing material, the heat-resistant temperature of the material can only be close to the glass transition temperature of the PLA and cannot be increased.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A biodegradable polylactic acid plastic uptake sheet comprises the following components in parts by weight: the composite material comprises, by weight, 50-95 parts of PLLA, 3-35 parts of PBAT, 3-10 parts of a compatilizer, 2-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler;
the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent;
the compatilizer is at least one of PBAT-g-GMA, PBAT-g-MHA and PBST-g-GMA;
the preparation method of the biodegradable polylactic acid plastic suction sheet comprises the steps of granulating, drying, extruding and forming and annealing in sequence; the extrusion forming device is a single-screw extruder, and the temperature of each part of the single-screw extruder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 200 ℃, the fourth zone is 210 ℃ and the head is 200 ℃.
2. The biodegradable polylactic acid plastic uptake sheet according to claim 1, wherein the annealing temperature is 150-160 ℃ and the annealing time is 20-40 s.
3. The biodegradable polylactic acid plastic uptake sheet according to claim 1, wherein the weight average molecular weight of PLLA is 30000-3000000 and the molecular weight distribution is 1.5-5.
4. The biodegradable polylactic acid plastic uptake sheet according to claim 1, wherein the weight average molecular weight of PBAT is 20000 to 130000, and the molecular weight distribution is 1.5 to 4.
5. The biodegradable polylactic acid blister sheet according to claim 1, wherein the dispersant comprises at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax, and polyethylene wax.
6. The biodegradable polylactic acid blister sheet according to claim 1, wherein the plasticizer comprises at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride.
7. The biodegradable polylactic acid plastic uptake sheet according to claim 1, wherein the coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum titanate coupling agent.
8. The biodegradable polylactic acid blister sheet according to claim 1, wherein the chain extender comprises a polyurethane chain extender and/or an epoxy chain extender.
9. The biodegradable polylactic acid blister sheet according to claim 8, wherein the polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
10. The biodegradable polylactic acid blister sheet according to claim 1, wherein the filler comprises at least one of calcium carbonate, montmorillonite and talc.
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| CN111718566A (en) * | 2019-03-22 | 2020-09-29 | 汉达精密电子(昆山)有限公司 | PLA/PBAT biodegradable composite material and product thereof |
| CN113801450A (en) * | 2021-11-10 | 2021-12-17 | 晋江市新迪新材料科技有限公司 | Full-biodegradable modified plastic for high-temperature-resistant extrusion straw product and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111718566A (en) * | 2019-03-22 | 2020-09-29 | 汉达精密电子(昆山)有限公司 | PLA/PBAT biodegradable composite material and product thereof |
| CN113801450A (en) * | 2021-11-10 | 2021-12-17 | 晋江市新迪新材料科技有限公司 | Full-biodegradable modified plastic for high-temperature-resistant extrusion straw product and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115612266A (en) * | 2022-09-30 | 2023-01-17 | 金发科技股份有限公司 | Full-biodegradable composition and preparation method and application thereof |
| CN115612266B (en) * | 2022-09-30 | 2024-03-22 | 金发科技股份有限公司 | Full-biodegradation composition and preparation method and application thereof |
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