CN115260717A - Polylactic acid foaming material, preparation method thereof and method for preparing polylactic acid foaming beads - Google Patents
Polylactic acid foaming material, preparation method thereof and method for preparing polylactic acid foaming beads Download PDFInfo
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- CN115260717A CN115260717A CN202210534929.7A CN202210534929A CN115260717A CN 115260717 A CN115260717 A CN 115260717A CN 202210534929 A CN202210534929 A CN 202210534929A CN 115260717 A CN115260717 A CN 115260717A
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- polylactic acid
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- pbat
- resin
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 111
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 110
- 238000005187 foaming Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000011324 bead Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 229920001434 poly(D-lactide) Polymers 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims abstract description 8
- 238000007348 radical reaction Methods 0.000 claims abstract description 3
- 229920001896 polybutyrate Polymers 0.000 claims description 29
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 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 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 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 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 230000006911 nucleation Effects 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 210000000497 foam cell Anatomy 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229920001432 poly(L-lactide) Polymers 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 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 5
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002101 nanobubble Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polybutylene succinate Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a polylactic acid foaming material, a preparation method thereof and a method for preparing polylactic acid foaming beads. The polylactic acid foaming material comprises the following components: 55-98 parts of PLA resin, 2-40 parts of PLA modifier and 0.2-5 parts of inorganic filler. The PLA modifier is prepared into PBAT-g-PDLA through free radical reaction, has high melt strength and nucleation function, is assisted with superfine inorganic filler, improves the melt strength of PLA alloy, induces foam cell nucleation, and is high in foaming multiplying power and uniform in foam cells.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-melt-strength and fast-crystallization polylactic acid foaming material and a preparation method thereof, and a preparation method of a polylactic acid bead foaming material.
Background
At present, the cushion packaging of express delivery trade, the quantity is very big and be non-degradable expanded material, retrieves the difficulty, causes certain influence to the environment. The development of degradable foaming materials in the future attracts more and more attention.
Polylactic acid (PLA) is a biodegradable material with excellent performance, can be molded by using traditional plastic processing equipment, has a degradation rate of more than 90 percent in 180 days in a composting environment after a product is used, is decomposed into small molecular substances harmless to the environment, is used in a foaming material, and has high strength and good buffering effect. But it is a linear structure and its expansion ratio is limited by low melt strength.
CN113736128A discloses a polylactic acid based foaming material and a preparation method thereof, in which a polylactic acid substrate comprises a stereo composite crystal and a homogeneous crystal, and the crystallinity of the stereo composite crystal is greater than or equal to 15%, the saturation treatment comprises a first saturation stage and a second saturation stage, the temperature of the first saturation stage is greater than or equal to the melting temperature of the homogeneous crystal and less than the melting temperature of the stereo composite crystal, and the temperature of the second saturation stage is less than the temperature of the first saturation stage; and then, carrying out pressure relief foaming on the saturated system to obtain the polylactic acid-based foaming material with high expansion ratio and excellent heat resistance. However, the material of the present invention has a complicated process and is difficult to control the expansion ratio.
CN112920583A discloses a poly L-lactic acid foaming material with rapid crystallization capability and a preparation method thereof, the alloy comprises poly L-lactic acid resin, PLLA-b-PDLA block copolymer and nano bubble nucleating agent, the foaming material is obtained by an injection molding process, and the alloy has the characteristics of higher heat resistance temperature, stable foaming, high cell density and the like. However, the material of the present invention does not have a branched structure and cannot achieve a high expansion ratio.
CN106916424A discloses a high-toughness heat-resistant full-biodegradable polylactic acid material and a preparation method thereof, wherein the alloy comprises industrial polylactic acid, dextrorotatory polylactic acid, poly (butylene glycol terephthalate-co-butylene glycol adipate) ester and a small amount of chain extender, and the prepared high-toughness full-biodegradable polylactic acid material has high strength, high toughness and high heat resistance. However, the material of the present invention does not have high melt strength characteristics and is not favorable for foaming.
CN109721977A discloses a high impact PLA/PBAT composite material and a preparation method thereof, the high impact PLA/PBAT composite material is prepared by blending polylactic acid and poly adipic acid-butylene terephthalate after chemical grafting modification, the preparation process is simple, and the cost is low. However, the material of the invention cannot promote the crystallization of polylactic acid and cannot be applied to polylactic acid foaming.
CN112552655A discloses a modified cellulose filled PBAT/PLA composition suitable for preparing a film, and preparation and application thereof, wherein polybutylene succinate grafted glycidyl methacrylate and polylactic acid grafted glycidyl methacrylate are selected as a compatibilizer of a PBAT/PLA system. However, the compatibilizer of this invention does not promote crystallization.
Disclosure of Invention
The invention provides a polylactic acid foaming material, a preparation method thereof and a method for preparing polylactic acid foaming beads. The prepared PLA foaming bead has high foaming ratio and uniform foam holes. High melt strength and quick crystallization.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a polylactic acid foam comprising the following composition:
55-98 parts, preferably 86-95 parts,
2-40 parts of PLA modifier, preferably 5-20 parts,
0.2 to 5 parts, preferably 0.5 to 4 parts,
the PLA modifier is in a PBAT-g-PDLA structure. Has higher melt strength and quick nucleation effect.
The PLA resin has a melt index of 2-8g/10min (190 ℃,2.16 kg), preferably 4-7g/10min (190 ℃,2.16 kg), preferably LX575, LX175 and LX530 of Total Corbion, 4032D, 8052D and 2002D of Natureworks, REVODE110, REVODE190 and REVODE101 of Zhejiang Hainan, FY801, FY802 and FY804 of Anhui Fengyo, and one or more of LX575 and LX175 of Total Corbion; more preferably one or more of 4032D, 8052D, 2002D from Natureworks corporation.
The inorganic filler is one or more of talcum powder, mica and montmorillonite, can play a role in assisting nucleation and strengthening, and can effectively improve the crystallinity of the material, so that the strength of the wall of a bubble hole is higher in the foaming process, and the bubble hole is not easy to collapse.
The mesh number of the inorganic filler of the present invention is 1000 to 10000 meshes, preferably 2000 to 9000 meshes.
The preparation method of the PLA modifier comprises the following steps:
(1) Performing dehydration condensation reaction on terephthalic acid (PTA), adipic Acid (AA) and 1, 4-Butanediol (BDO) under the action of a catalyst to obtain PBAT resin;
(2) Adding a terminating agent glycidyl methacrylate, reacting, and terminating the PBAT resin to obtain terminated PBAT resin;
(3) And reacting the terminated PBAT resin with PDLA in a double-screw extruder under the action of an initiator to obtain the PLA modifier.
The catalyst in the step (1) is one or more of tetrabutyl titanate and antimony trioxide.
In step (1) of the present invention, the molar ratio of PTA to AA is 1:0.9-1:1.25, preferably 1:1-1:1.2.
in step (1) of the present invention, the molar ratio of the sum of the molar amounts of PTA and AA to the molar amount of BDO is 1:1-1:1.5, preferably 1:1.1-1:1.4.
in the step (1) of the present invention, the molar ratio of BDO to catalyst is 3000:1-1000: 1, preferably 2800:1-1400:1.
in the step (1), the dehydration condensation reaction temperature is 160-200 ℃, the reaction time is 0.5-3h, preferably, the reaction temperature is 170-190 ℃, and the reaction time is 1-2h.
In step (2) of the present invention, the molar ratio of BDO to glycidyl methacrylate in step (1) is 30:1-10:1, preferably 28:1-14:1.
in step (2) of the present invention, the weight average molecular weight of the terminated PBAT resin is 10000 to 50000, preferably 20000 to 40000. Too high molecular weight has low reactivity, which is not beneficial to the subsequent free radical grafting reaction; too low a molecular weight results in low branching, which is detrimental to foaming.
In the step (2), the reaction temperature is 160-200 ℃, the reaction time is 0.5-2h, the preferable reaction temperature is 170-190 ℃, and the reaction time is 0.7-1.5h. Suitable reaction temperatures and reaction times readily yield resins of corresponding weight average molecular weights.
In step (3) of the present invention, PDLA: blocked PBAT resin: the mass ratio of the initiator is 1000: (100-800): (0.2-2), preferably, PDLA: blocked PBAT resin: the mass ratio of the initiator is 1000: (200-600): (0.5-1.8).
In the step (3), the initiator is one or more of dicumyl peroxide, benzoyl peroxide and methyl ethyl ketone peroxide, and the preferred initiator is dicumyl peroxide, and the initiator can initiate free radical reaction.
In step (3) of the present invention, the PDLA is one or more of 070D and 120D, preferably 070D, of Total Corbion.
In the step (3) of the present invention, the temperature of the twin-screw extruder is 160-210 ℃, the screw rotation speed is 200-700rpm, preferably, the temperature of the twin-screw extruder is 170-200 ℃, and the screw rotation speed is 300-500rpm. The material is not easily degraded by high-temperature heat due to the overhigh double-screw extrusion temperature, and the reaction is not facilitated; excessively low twin-screw extrusion temperature affects radical reactivity; too high a screw speed results in a material that is susceptible to shear degradation; too low screw rotation speed is not beneficial to dispersion, and the reaction efficiency is low.
Another object of the present invention is to provide a method for preparing a polylactic acid foamed material.
The method for preparing the polylactic acid foaming material comprises the following steps:
mixing PLA resin, PLA modifier and inorganic filler, adding into a main feeding port of a double-screw extruder, melting, extruding, cooling, granulating and drying.
In the method for preparing the polylactic acid foaming material, the rotating speed of a double-screw extruder is 200-700 r/min, and the extrusion temperature is 150-200 ℃.
In the method for preparing the polylactic acid foaming material, the length of the obtained particles is controlled to be 1-3mm, and the diameter is controlled to be 0.2-1mm.
A method of preparing polylactic acid expanded beads comprising the steps of: and (3) performing bead foaming on the polylactic acid foaming material in a high-pressure reaction kettle.
The bead foaming step is that a high-pressure reaction kettle is vacuumized to remove moisture, a foaming agent is pressurized to 6-9MPa by using an injection pump, then the foamed particles are heated to 80-120 ℃, saturated for 60-90min, decompressed and cooled to obtain bead foam.
The foaming agent is one or more of supercritical carbon dioxide and supercritical nitrogen.
Compared with the prior art, the invention has the following technical advantages:
1) Because PLA is a straight chain structure, the melt strength is low, a foaming material with high foaming ratio is not easy to obtain, and a chain extender is usually added to improve the melt strength of the material. At the same time, a nucleating agent is also required to be added, so that a nucleating site is provided in the foaming process to nucleate foam cells. According to the invention, through the structural design of PLA, the self-made PLA modified resin is of a PBAT-g-PDLA structure, has high melt strength and nucleation effect, and in the blending process with PLA, the PDLA part in the PLA modifier can form a discrete structure complex composite crystal with the PLLA, so that a crystallization site is provided, the nucleation of foam cells can be induced, the crystallinity of the material is improved, and the heat resistance is improved.
(2) The PLA modifier is a branched structure and is assisted with a small amount of inorganic filler, so that the melt strength is higher, the melt stretch hardening phenomenon can resist the biaxial stretching effect formed in the cell growth process, and the gas core grown at a higher foaming temperature is stabilized.
(3) Utilizing environmentally friendly supercritical CO2Foaming agent is used for foaming the prepared PLA alloy, and the apparent density of the obtained foaming beads is 0.04-0.06g/cm3And the foaming multiplying power is 20-30 times. The average cell size is 20-40 μm, and the density of the cells is 4 x 108-7*108Per cm3. Can be used in the field of buffer packaging.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
In each of the examples and comparative examples, the main raw material sources are as follows in table 1:
TABLE 1 raw materials and sources
| Raw materials | Manufacturer of the product |
| PLLA (LX 175), melt index 4g/10min (190 ℃,2.16 kg) | Dodarke Bien polylactic acid Co Ltd |
| PDLA(070D) | Doudaco Bien polylactic acid Co Ltd |
| PLLA (FY 801), molten finger 8g/10min (190 ℃,2.16 kg) | ANHUI BBCA GROUP Co.,Ltd. |
| PLLA (4032D), molten finger 4g/10min (190 ℃,2.16 kg) | Natureworks Inc |
| TH801T | Xinjiang blue mountain Tunghe science and technology Co Ltd |
| Talcum powder, cimtuff 9103D (3000 mesh) | Guiguangshiba powder Material Limited liability Co Ltd |
| Talcum powder, performaflex D (8000 mesh) | Guiguangshiba powder Material Limited liability Co Ltd |
| Terephthalic acid (TPA) | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Adipic acid | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| 1, 4-butanediol | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Tetrabutyl titanate | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Glycidyl methacrylate | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Dicumyl peroxide | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Methyl ethyl ketone peroxide | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
The performance test parameters and corresponding test methods for PLA alloys and PLA foams are as follows:
TABLE 2 Performance test methods
| Content of test | Unit of | Test method |
| Melt index | g/10min | ISO 1133 |
| Melt strength | F/mN | ISO 16790 |
| Expansion ratio | GB/T 6343 | |
| Average cell size | μm | GB/T 12811 |
| Cell density | Per cm3 | GB/T 12811 |
| Degree of crystallinity | ％ | ISO 11357 |
The processing equipment is as follows:
a twin-screw extruder, koilong, model number ZSK 26Mc 18, length-diameter ratio of 52, screw diameter of 26cm; the volume of the high-pressure reaction kettle is 10L.
The test equipment used was:
the German Gottfert melt index instrument has the test conditions of 190 ℃ and 21.6kg (the melt strength of the material prepared at this time is very high and cannot be measured under the conditions of 190 ℃ and 2.16kg, so the test conditions are set to be 190 ℃ and 21.6 kg);
germany Gottfert melt Strength apparatus, speed range is 100cm/s;
foam density tester of the tesile instrument;
a zeiss EVO series scanning electron microscope.
A Mettler-Tollidol differential scanning calorimeter DSC3 of Switzerland, a heating rate of 10 ℃/min.
Example 1
(1) PLA modified resin A:
a. 83g of PTA, 73g of AA, 99g of BDO and 0.25g of tetrabutyl titanate are put into a three-neck flask, fully stirred, the temperature is controlled at 170 ℃, the reaction is carried out for 1 hour, then 10.4g of glycidyl methacrylate is added into the three-neck flask, the reaction is continued for 0.7 hour, and the mixture is cooled and dried to obtain the end-capped PBAT resin A with the molecular weight of 30000.
b. 200g of terminated PBAT resin A, 1000g of 070D and 0.5g of dicumyl peroxide are put into a double-screw extruder, and the extrusion conditions are as follows: the screw rotating speed is 200rpm, and the screw temperature is set from the feed opening to the machine head in a segmented mode as follows: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃; obtaining the PLA modifier A.
(2) Preparation of PLA foaming material
The PLA modified resin, the PLA resin and the talcum powder are added into a double-screw extruder according to the raw material dosage shown in the table 3, and the extrusion conditions are as follows: the screw rotating speed is 200rpm, and the screw temperature is set from the feed opening to the machine head in a segmented mode as follows: 150 deg.C, 160 deg.C, 170 deg.C, 175 deg.C, 180 deg.C, 185 deg.C, 190 deg.C, 200 deg.C; cooling the extruded material in a water tank of an extruder, pelletizing, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain the PLA alloy, wherein the particle diameter is 0.2mm, and the particle length is 1mm;
(3) Preparation of PLA expanded beads
Adding a PLA foaming material into a foaming autoclave, vacuumizing to remove moisture, and injecting supercritical CO through a syringe pump2Pressurizing the mixture at 6MPa, heating the mixture to 90 ℃, quickly releasing the pressure after the mixture is saturated for 40min, and collecting PLA bead foam.
Example 2
(1) PLA modified resin B:
a. 83g of PTA, 73g of AA, 112.5g of BDO and 0.17g of tetrabutyl titanate are put into a three-neck flask, fully stirred, the temperature is controlled at 180 ℃, reaction is carried out for 2h, then 7.1g of glycidyl methacrylate is added into the three-neck flask, reaction is continued for 1h, cooling and drying are carried out, and the end-capped PBAT resin A with the molecular weight of 40000 is obtained.
b. 400g of terminated PBAT resin B, 1000g of 070D and 1g of dicumyl peroxide are put into a double-screw extruder, and the extrusion conditions are as follows: the rotating speed of the screw is 300rpm, and the temperature of the screw is set from the feed opening to the machine head in a segmented mode as follows: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃; obtaining PLA modified resin B.
(2) Preparation of PLA foaming material
Adding PLA modified resin B, PLA resin and talcum powder into a double-screw extruder according to the raw material dosage shown in Table 3, wherein the extrusion conditions are as follows: the rotating speed of the screw is 300rpm, and the temperature of the screw is set from the feed opening to the machine head in a segmented mode as follows: 170 ℃, 175 ℃, 185 ℃, 190 ℃,200 ℃ and 200 ℃; cooling the extruded material in a water tank of an extruder, pelletizing and drying in a vacuum oven at 90 ℃ for 4 hours to obtain the PLA alloy, wherein the particle diameter is 0.5mm, and the particle length is 2mm;
(3) Preparation of PLA expanded beads
Adding PLA foaming material into a foaming autoclave, vacuumizing to remove moisture, and injecting supercritical CO through a syringe pump2Pressurizing the mixture at 7.5MPa, heating the mixture to 100 ℃, quickly releasing the pressure after saturation for 60min, and collecting PLA bead foam.
Example 3
(1) PLA modified resin C:
a. adding 74.7g of PTA, 80.3g of AA, 126g of BDO and 0.17g of tetrabutyl titanate into a three-neck flask, fully stirring, controlling the temperature at 190 ℃, reacting for 2.5h, then adding 7.1g of glycidyl methacrylate into the three-neck flask, continuing to react for 1.5h, cooling and drying to obtain the glycidyl methacrylate terminated oligomeric PBAT with the molecular weight of 25000.
b. 600g of terminated PBAT resin C, 1000g of 070D and 1.8g of methyl ethyl ketone peroxide are put into a double-screw extruder, and the extrusion conditions are as follows: the screw rotating speed is 500rpm, and the screw temperature is set from the feed opening to the machine head in a segmented mode as follows: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃, 210 ℃ and 210 ℃; obtaining the PLA modified resin C.
(2) Preparation of PLA foaming material
The PLA modified resin C, the PLLA and the talcum powder are added into a double-screw extruder according to the raw material dosage shown in the table 3, and the extrusion conditions are as follows: the screw rotating speed is 500rpm, and the screw temperature is set from the feed opening to the machine head in a segmented mode as follows: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃; cooling the extruded material in a water tank of an extruder, pelletizing, and drying in a vacuum oven at 90 ℃ for 4 hours to obtain the PLA alloy, wherein the particle diameter is 0.8mm, and the particle length is 2.5mm;
(3) Preparation of PLA expanded beads
Adding PLA foaming material into a foaming autoclave, vacuumizing to remove moisture, and injecting supercritical CO through a syringe pump2Pressurizing it at a pressure of 9MPa and lThe temperature is increased to 115 ℃, and after 80min of saturation, the pressure is rapidly released, and PLA bead foam is collected.
Comparative example 1
This comparative example directly replaces the PLA modifier with a commercially available PBAT and prepares PLA expanded beads as in example 2, except that the formulation in table 3 is different.
Comparative example 2
This comparative example directly replaces the PLA modifier with commercially available PBAT and PDLA and PLA expanded beads were prepared as in example 2, except that the formulation in table 3 was different.
Comparative example 3
This comparative example did not add a PLA modifier and PLA expanded beads were prepared as in example 2, except that the formulation in table 3 was different.
The results of the property test of the foamed sheets obtained in examples 1 to 3 and comparative examples 1 to 2 are shown in Table 4.
TABLE 3 raw materials and amounts (Kg) used in examples 1-3 (S1-S3) and comparative examples 1-3 (D1-D3)
| Raw material | S1 | S2 | S3 | D1 | D2 | D3 |
| LX175 | 94.4 | |||||
| 4032D | 77.5 | 77.5 | 77.5 | 97.5 | ||
| FY801 | 60.5 | |||||
| PLA modifier A | 5 | |||||
| PLA modifier B | 20 | |||||
| PLA modifier C | 35 | |||||
| 070D | 10 | |||||
| Cimtuff 9103D (3000 mesh) | 0.6 | 2.5 | 2.5 | 2.5 | 2.5 | |
| Performaflex D (8000 mesh) | 4.5 | |||||
| TH801T | 20 | 10 |
TABLE 4 results of product Performance test of examples 1-4 (S1-S3) and comparative examples 1-3 (D1-D3)
As can be seen from comparative example 1 and examples 1-3, the direct addition of commercially available PBAT did not result in a rapid nucleation effect, the average cell size was large, and the crystallinity was low. As can be seen from comparative example 2 and examples 1 to 3, if commercially available PBAT and PDLA are directly added, phase separation easily occurs due to poor compatibility of PLA and PBAT, and the foamed PLA foam cells are not uniform. As can be seen from comparative example 3 and examples 1-3, no PLA modifier was added, there was no faster nucleation, the average cell size was large and the cell strength was low. Examples 1 to 3 show that the prepared PLA expanded beads have high expansion ratio and uniform cells. Supercritical CO2When the polyurethane foaming agent is used as a foaming agent, the foaming ratio can reach 30 times, the foam holes are uniform, and the polyurethane foaming agent has a strong market application value.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polylactic acid foam comprising the following composition:
55-98 parts, preferably 86-95 parts,
2-40 parts of PLA modifier, preferably 5-20 parts,
0.2 to 5 parts, preferably 0.5 to 4 parts,
the PLA modifier is in a PBAT-g-PDLA structure.
2. Polylactic acid foam according to claim 1, wherein the PLA resin has a melt index of 2-8g/10min and is tested at 190 ℃ under 2.16kg, preferably 4-7g/10min, preferably at one or more of LX575, LX175, LX530 from Total Corbion, 4032D, 8052D, 2002D from Natureworks, revolute marine, revolute 110, revolute 190, revolute 101, FY801 from anfeng, FY801, FY802, FY804, LX575, LX175 from Total Corbion.
3. The polylactic acid foaming material according to claim 1, wherein the inorganic filler is one or more of talcum powder, mica and montmorillonite.
4. A polylactic acid foamed material according to any one of claims 1 to 3, wherein the mesh number of the inorganic filler is 1000 to 10000 mesh.
5. The polylactic acid foamed material according to claim 1, wherein the PLA modifier is prepared by a radical reaction of a terminated PBAT resin with PDLA under the action of an initiator.
6. The polylactic acid foaming material according to claim 1, wherein the preparation method of the PLA modifier comprises the following steps:
(1) Dehydrating and condensing terephthalic acid, adipic acid and 1, 4-butanediol under the action of a catalyst to obtain PBAT resin;
(2) Adding a terminating agent glycidyl methacrylate, reacting, and terminating the PBAT resin to obtain a terminated PBAT resin;
(3) And extruding the end-capped PBAT resin and the PDLA in a double-screw extruder under the action of an initiator to obtain the PLA modifier.
7. The polylactic acid foamed material according to claim 6, wherein in the step (2), the molar ratio of 1, 4-butanediol to glycidyl methacrylate in the step (1) is 30:1-10:1, preferably 28:1-14:1.
8. the foamed polylactic acid material according to claim 6, wherein in the step (3), the ratio of PDLA: blocked PBAT resin: the mass ratio of the initiator is 1000: (100-800): (0.2-2), preferably, PDLA: blocked PBAT resin: the mass ratio of the initiator is 1000: (200-600): (0.5-1.8).
9. A method for preparing the polylactic acid foamed material according to any one of claims 1 to 8, comprising the steps of: mixing PLA resin, PLA modifier and inorganic filler, adding into a main feeding port of a double-screw extruder, melting, extruding, cooling, granulating and drying.
10. A method of preparing polylactic acid expanded beads comprising the steps of: pressurizing the polylactic acid foaming material of any one of claims 1 to 8 to 6 to 9MPa of foaming agent in a high-pressure reaction kettle, heating to 80 to 120 ℃, saturating for 60 to 90min, decompressing and cooling.
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Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090008899A (en) * | 2007-07-19 | 2009-01-22 | 정지수 | Polymer composition of polylactic acid, foam sheet using the same, manufacturing method thereof and use of foam-molding product thereby |
| JP2012025869A (en) * | 2010-07-26 | 2012-02-09 | Jsp Corp | Method for producing polylactic acid-based resin foamed particle |
| US20160039990A1 (en) * | 2013-03-28 | 2016-02-11 | Synbra Technology B.V. | A method for the preparation of pla bead foams |
| JP6043897B1 (en) * | 2015-11-06 | 2016-12-14 | バンドー化学株式会社 | Method for producing foam molded article and foam molded article |
| CN106916421A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material |
| JP2017165906A (en) * | 2016-03-17 | 2017-09-21 | バンドー化学株式会社 | Foaming resin composition and foam molding |
| CN109721977A (en) * | 2018-12-21 | 2019-05-07 | 辽宁石油化工大学 | A kind of high-impact PLA/PBAT composite material and preparation method |
| CN110041677A (en) * | 2019-04-30 | 2019-07-23 | 常州大学 | A kind of complete biodegradable crosslinking polylactic acid base thermoplastic elastomer and preparation method thereof |
| CN110079065A (en) * | 2019-04-30 | 2019-08-02 | 常州大学 | A kind of high tenacity PLA/PBAT blend alloy and preparation method thereof |
| US20200024243A1 (en) * | 2017-12-01 | 2020-01-23 | Ningbo Homelink Eco-Itech Co., Ltd. | Heat-resistant polylactic acid continuously-extruded foamed material and preparation method thereof |
| CN111286070A (en) * | 2020-02-11 | 2020-06-16 | 中国科学院宁波材料技术与工程研究所 | Supercritical fluid injection-molded foamed polylactic acid foam material and preparation method thereof |
| CN112920583A (en) * | 2021-04-14 | 2021-06-08 | 中国科学院长春应用化学研究所 | Poly-L-lactic acid foaming material with rapid crystallization capacity and preparation method thereof |
| CN113214618A (en) * | 2021-04-14 | 2021-08-06 | 何顺伦 | Food-grade heat-resistant PLA (polylactic acid) foam material and preparation method thereof |
| CN113354929A (en) * | 2021-06-07 | 2021-09-07 | 万华化学（宁波）有限公司 | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material |
| WO2021232668A1 (en) * | 2020-05-20 | 2021-11-25 | 安踏（中国）有限公司 | Biodegradable foam midsole material and preparation method therefor |
| CN113736129A (en) * | 2021-09-18 | 2021-12-03 | 南京工业大学 | Lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and preparation method thereof |
| CN113736228A (en) * | 2021-09-07 | 2021-12-03 | 万华化学（宁波）有限公司 | High-magnification PBAT foaming bead and preparation method thereof |
| CN113736226A (en) * | 2021-09-02 | 2021-12-03 | 万华化学（宁波）有限公司 | Degradable PBAT composite film and preparation method thereof |
| KR20220017791A (en) * | 2020-08-05 | 2022-02-14 | 최길배 | Pla-pbat block copolymer, preparation thereof and biodegradable resin composition comprising the same |
-
2022
- 2022-05-17 CN CN202210534929.7A patent/CN115260717B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090008899A (en) * | 2007-07-19 | 2009-01-22 | 정지수 | Polymer composition of polylactic acid, foam sheet using the same, manufacturing method thereof and use of foam-molding product thereby |
| JP2012025869A (en) * | 2010-07-26 | 2012-02-09 | Jsp Corp | Method for producing polylactic acid-based resin foamed particle |
| US20160039990A1 (en) * | 2013-03-28 | 2016-02-11 | Synbra Technology B.V. | A method for the preparation of pla bead foams |
| JP6043897B1 (en) * | 2015-11-06 | 2016-12-14 | バンドー化学株式会社 | Method for producing foam molded article and foam molded article |
| JP2017165906A (en) * | 2016-03-17 | 2017-09-21 | バンドー化学株式会社 | Foaming resin composition and foam molding |
| CN106916421A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material |
| US20200024243A1 (en) * | 2017-12-01 | 2020-01-23 | Ningbo Homelink Eco-Itech Co., Ltd. | Heat-resistant polylactic acid continuously-extruded foamed material and preparation method thereof |
| CN109721977A (en) * | 2018-12-21 | 2019-05-07 | 辽宁石油化工大学 | A kind of high-impact PLA/PBAT composite material and preparation method |
| CN110079065A (en) * | 2019-04-30 | 2019-08-02 | 常州大学 | A kind of high tenacity PLA/PBAT blend alloy and preparation method thereof |
| CN110041677A (en) * | 2019-04-30 | 2019-07-23 | 常州大学 | A kind of complete biodegradable crosslinking polylactic acid base thermoplastic elastomer and preparation method thereof |
| CN111286070A (en) * | 2020-02-11 | 2020-06-16 | 中国科学院宁波材料技术与工程研究所 | Supercritical fluid injection-molded foamed polylactic acid foam material and preparation method thereof |
| WO2021232668A1 (en) * | 2020-05-20 | 2021-11-25 | 安踏（中国）有限公司 | Biodegradable foam midsole material and preparation method therefor |
| KR20220017791A (en) * | 2020-08-05 | 2022-02-14 | 최길배 | Pla-pbat block copolymer, preparation thereof and biodegradable resin composition comprising the same |
| CN112920583A (en) * | 2021-04-14 | 2021-06-08 | 中国科学院长春应用化学研究所 | Poly-L-lactic acid foaming material with rapid crystallization capacity and preparation method thereof |
| CN113214618A (en) * | 2021-04-14 | 2021-08-06 | 何顺伦 | Food-grade heat-resistant PLA (polylactic acid) foam material and preparation method thereof |
| CN113354929A (en) * | 2021-06-07 | 2021-09-07 | 万华化学（宁波）有限公司 | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material |
| CN113736226A (en) * | 2021-09-02 | 2021-12-03 | 万华化学（宁波）有限公司 | Degradable PBAT composite film and preparation method thereof |
| CN113736228A (en) * | 2021-09-07 | 2021-12-03 | 万华化学（宁波）有限公司 | High-magnification PBAT foaming bead and preparation method thereof |
| CN113736129A (en) * | 2021-09-18 | 2021-12-03 | 南京工业大学 | Lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| TING GU等: "Effect of PLA-g-GMA on the Thermal, Rheological and Physical Behavior of PLAPBAT Blends", 《POLYMER SCIENCE》, pages 317 - 324 * |
| 刘申;王海刚;王清文;: "聚苯乙烯基发泡木塑复合材料的制备与性能", 东北林业大学学报, no. 10, pages 69 - 71 * |
| 王鑫;石敏;余晓磊;彭少贤;赵西坡;: "聚己二酸对苯二甲酸丁二酯(PBAT)共混改性聚乳酸(PLA)高性能全生物降解复合材料研究进展", 材料导报, no. 11, pages 128 - 140 * |
| 谢丽锦等: "熔融共混制备PLA-g-MAH/EP对PLA/PBAT复合材料性能的影响", 《高分子材料科学与工程》, pages 74 - 76 * |
| 马调调;: "PBAT/OMMT复合材料的力学性能研究", 橡塑技术与装备, no. 10, pages 7 - 14 * |
| 齐迎珍;邹俊;徐海青;: "PBAT/PLA复合材料的制备及其微球发泡行为研究", 塑料科技, no. 10, pages 5 - 10 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116284954A (en) * | 2023-03-06 | 2023-06-23 | 江苏越升科技股份有限公司 | Biodegradable polymer foaming bead capable of being formed by steam compression molding |
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