CN115260717B - Polylactic acid foam material, preparation method thereof and method for preparing polylactic acid foam beads - Google Patents
Polylactic acid foam material, preparation method thereof and method for preparing polylactic acid foam beads Download PDFInfo
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- CN115260717B CN115260717B CN202210534929.7A CN202210534929A CN115260717B CN 115260717 B CN115260717 B CN 115260717B CN 202210534929 A CN202210534929 A CN 202210534929A CN 115260717 B CN115260717 B CN 115260717B
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 115
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 114
- 239000011324 bead Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000006261 foam material Substances 0.000 title claims abstract description 16
- 239000006260 foam Substances 0.000 title abstract description 18
- 238000005187 foaming Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000003607 modifier Substances 0.000 claims abstract description 24
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- 238000007348 radical reaction Methods 0.000 claims abstract description 3
- 229920001896 polybutyrate Polymers 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000203 mixture Substances 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
- 238000001035 drying Methods 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000003054 catalyst Substances 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
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 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
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000454 talc Substances 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 9
- 238000010899 nucleation Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 10
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 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 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
- 239000002131 composite material Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 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
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011056 performance test Methods 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
- 238000007792 addition Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- -1 polybutylene succinate Polymers 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
- 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
- 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
- 229910002092 carbon dioxide Inorganic materials 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
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 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
- 229920005586 poly(adipic acid) 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
- 238000011084 recovery Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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 foam material, a preparation method thereof and a method for preparing polylactic acid foam 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 by a free radical reaction, has the functions of high melt strength and nucleation, and is supplemented with superfine inorganic filler, so that the melt strength of PLA alloy is improved, cell nucleation is induced, and the prepared PLA foaming beads have high foaming multiplying power and uniform 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, buffer packaging in the express industry has large consumption and is made of non-degradable foaming materials, recovery is difficult, and certain influence is caused on the environment. The development of degradable foam materials in the future is attracting 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% in 180 days in a composting environment after being 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 low melt strength limits its expansion ratio.
CN113736128A discloses a polylactic acid-based foaming material and a preparation method thereof, wherein the polylactic acid base material comprises a stereocomplex crystal and a homogeneous crystal, the crystallinity of the stereocomplex 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 the melting temperature of the small Yu Ligou composite crystal, and the temperature of the second saturation stage is less than the temperature of the first saturation stage; and then the saturated system is subjected to pressure relief foaming, so that the polylactic acid-based foaming material is high in expansion rate and excellent in heat resistance. However, the material of the invention has complex process and is difficult to control the foaming 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 through injection molding process, and the alloy has the characteristics of higher heat-resistant temperature, stable foaming, high cell density and the like. However, the material of the invention does not have a branched structure, and cannot achieve high foaming ratio.
CN106916424a discloses a high-toughness heat-resistant fully biodegradable polylactic acid material and a preparation method thereof, the alloy comprises industrial polylactic acid, dextrorotation polylactic acid, poly (butylene terephthalate-co-butylene adipate) ester and a small amount of chain extender, and the prepared high-toughness fully biodegradable polylactic acid material has high strength, high toughness and high heat resistance. However, the material of the invention does not have high melt strength characteristics, which is disadvantageous for foaming.
CN109721977a discloses a high impact PLA/PBAT composite material and a preparation method thereof, and the high impact PLA/PBAT composite material is prepared by blending polylactic acid and chemically grafted and modified poly (adipic acid) -butylene terephthalate, and has the advantages of simple preparation process and low cost. However, the material of the invention cannot promote the crystallization of polylactic acid and cannot be applied to the foaming of polylactic acid.
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 the present invention does not promote crystallization.
Disclosure of Invention
The invention provides a polylactic acid foam material, a preparation method thereof and a method for preparing polylactic acid foam beads. The prepared PLA foaming beads have high foaming multiplying power and uniform foam holes. High melt strength and quick crystallization.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a polylactic acid foam material comprising the following composition:
55 to 98 parts, preferably 86 to 95 parts,
2 to 40 parts, preferably 5 to 20 parts,
0.2 to 5 parts, preferably 0.5 to 4 parts,
the PLA modifier has 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 one or more of LX575, LX175, LX530 of Total Corbion, 4032D, 8052D, 2002D of Nature corporation, REVODE110, REVODE190, REVODE101 of Zhejiang sea, FY801, FY802, FY804 of Anhuifeng original, LX575, LX175 of Total Corbion; more preferably one or more of Nature's companies 4032D, 8052D, 2002D.
The inorganic filler is one or more of talcum powder, mica and montmorillonite, can play a role in auxiliary nucleation and enhancement, and can more effectively improve the crystallinity of the material, so that the strength of the wall of the foam hole in the foaming process is higher, and the foam hole is not easy to collapse.
The mesh number of the inorganic filler of the present invention is 1000 to 10000 mesh, preferably 2000 to 9000 mesh.
The preparation method of the PLA modifier provided by the invention comprises the following steps:
(1) Carrying out 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 capping agent glycidyl methacrylate, reacting, and capping the PBAT resin to obtain capped PBAT resin;
(3) And reacting the end-capped PBAT resin and 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 antimonous oxide.
In the step (1), the molar ratio of PTA to AA is 1:0.9-1:1.25, preferably 1:1-1:1.2.
in the step (1), the molar ratio of the sum of the molar amounts of PTA and AA to BDO is 1:1-1:1.5, preferably 1:1.1-1:1.4.
in the step (1), the molar ratio of BDO to the 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 the step (2), the molar ratio of BDO to glycidyl methacrylate in the step (1) is 30:1-10:1, preferably 28:1-14:1.
in the step (2) of the present invention, the weight average molecular weight of the end-capped PBAT resin is 10000-50000, preferably 20000-40000. Too high molecular weight has low reactivity, and is unfavorable for subsequent free radical grafting reaction; too low a molecular weight results in a low degree of branching, which is detrimental to foaming.
In the step (2), the reaction temperature is 160-200 ℃, the reaction time is 0.5-2h, preferably the reaction temperature is 170-190 ℃, and the reaction time is 0.7-1.5h. Suitable reaction temperatures and reaction times readily result in resins of corresponding weight average molecular weights.
In the step (3) of the invention, PDLA: end-capped PBAT resin: the mass ratio of the initiator is 1000: (100-800): (0.2-2), preferably PDLA: end-capped 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 preferable initiator is dicumyl peroxide, and the initiator can initiate free radical reaction.
In the step (3) of the present invention, the PDLA is one or more of 070D and 120D of Total cobion company, preferably 070D.
In the step (3) of the invention, the temperature of the twin-screw extruder is 160-210 ℃, the screw rotating speed is 200-700rpm, preferably, the temperature of the twin-screw extruder is 170-200 ℃, and the screw rotating speed is 300-500rpm. Too high a double-screw extrusion temperature causes high-temperature thermal degradation of the material, which is unfavorable for the reaction; too low a twin screw extrusion temperature affects free radical reactivity; too high a screw speed results in materials that are susceptible to shear degradation; too low a screw speed is unfavorable for dispersion and reaction efficiency is low.
Another object of the present invention is to provide a method for preparing a polylactic acid foam 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 the double-screw extruder is 200-700 revolutions per minute, 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 to vacuumize a high-pressure reaction kettle to remove water, pressurize a foaming agent to 6-9MPa by using an injection pump, then heat the foaming particles to 80-120 ℃, saturate for 60-90min, decompress and cool to obtain the 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 of a straight-chain structure, the melt strength is low, and a foaming material with high foaming multiplying power is not easy to obtain, and usually a chain extender is required to be added, so that the melt strength of the material is improved. At the same time, a nucleating agent is also required to be added to provide nucleation sites for nucleating cells during the foaming process. According to the invention, through PLA structure design, the self-made PLA modified resin is of a PBAT-g-PDLA structure, and has the effects of high melt strength and nucleation, and in the blending process with PLA, the PDLA part in the PLA modifier and the PLLA can form a part of a constitutive complex composite crystal, so that crystallization sites are provided, the nucleation of cells can be induced, the crystallinity of the material is improved, and the heat resistance is improved.
(2) The PLA modifier is of a branched structure, and a small amount of inorganic filler is assisted, so that the PLA modifier has higher melt strength, and the phenomenon of melt stretch hardening can resist the biaxial stretching effect formed in the process of cell growth, so that the gas core growing stably at a higher foaming temperature.
(3) Supercritical CO utilizing environmental protection 2 Foaming the prepared PLA alloy by using a foaming agent to obtain foamed beads with apparent density of 0.04-0.06g/cm 3 The foaming multiplying power is 20-30 times. Average cell size of 20-40 μm, cell density of 4 x 10 8 -7*10 8 Individual/cm 3 . Can be used in the field of cushion packaging.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
In each of the examples and comparative examples, the main raw material sources are shown in table 1 below:
TABLE 1 raw materials and sources
| Raw materials | Manufacturer' s |
| PLLA (LX 175), melt finger 4g/10min (190 ℃,2.16 kg) | Dadaceae Bien polylactic acid Co Ltd |
| PDLA(070D) | Dadaceae Bien polylactic acid Co Ltd |
| PLLA (FY 801), 8g/10min of melt finger (190 ℃,2.16 kg) | ANHUI BBCA GROUP Co.,Ltd. |
| PLLA (4032D), melt finger 4g/10min (190 ℃,2.16 kg) | Nature eworks Co |
| TH801T | Xinjiang blue mountain Tun river science and technology Co., ltd |
| Talcum powder, cimtuff 9103D (3000 mesh) | Gui Anshen bar powder Material Limited company |
| Talcum powder, performaflex D (8000 mesh) | Gui Anshen bar powder Material Limited company |
| Terephthalic acid | 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 Aba Ding Shenghua technologyStock 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 in table 2:
table 2 performance testing method
| Content of test | Unit (B) | Test method |
| Melt index | g/10min | ISO 1133 |
| Melt strength | F/mN | ISO 16790 |
| Expansion ratio | GB/T 6343 | |
| Average cell sizeSize of the device | μm | GB/T 12811 |
| Cell density of | Individual/cm 3 | GB/T 12811 |
| Crystallinity degree | ％ | ISO 11357 |
The processing equipment used is as follows:
a twin-screw extruder, keplong, model ZSK 26Mc 18, length-diameter ratio of 52, screw diameter of 26cm; the volume of the high-pressure reaction kettle, wiHai Xinyuan chemical machinery Co., ltd, is 10L.
The test equipment used was:
the test condition of the Gottfert melt index instrument in Germany is 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 that the test condition is set to be 190 ℃ and 21.6 kg);
the Gottfert melt strength instrument, germany, has a speed range of 100cm/s;
foam density tester of the Qinshite instrument;
zeiss EVO series scanning electron microscope.
Switzerland Metrele-tolidol differential scanning calorimeter DSC3, heating rate 10 ℃/min.
Example 1
(1) PLA modified resin A:
a. 83g PTA, 73. 73gAA, 99g BDO and 0.25g tetrabutyl titanate are put into a three-neck flask, fully stirred, the temperature is controlled at 170 ℃, the reaction is carried out for 1h, then 10.4g glycidyl methacrylate is added into the three-neck flask, the reaction is continued for 0.7h, the cooling and the drying are carried out, and the end-capped PBAT resin A with the molecular weight of 30000 is obtained.
b. 200g of end-capped PBAT resin A, 1000g of 070D and 0.5g of dicumyl peroxide are put into a double-screw extruder, and extrusion conditions are as follows: the screw rotation speed is 200rpm, and the screw temperature is set as from the feed opening to the machine head section: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃; obtaining PLA modifier A.
(2) PLA foaming material preparation
The PLA modified resin, PLA resin and talcum powder were fed into a twin screw extruder with reference to the raw material amounts of Table 3, and extrusion conditions were: the screw rotation speed is 200rpm, and the screw temperature is set as from the feed opening to the machine head section: 150 ℃, 160 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃; cooling the extruded material in an extruder water tank, granulating, 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) PLA foam bead preparation
Adding PLA foaming material into a foaming autoclave, vacuumizing to remove water, injecting supercritical CO by an injection pump 2 The mixture was pressurized at a pressure of 6MPa and warmed to 90℃and after saturation for 40min, the pressure was rapidly released and the PLA bead foam was collected.
Example 2
(1) PLA modified resin B:
a. 83g PTA, 73. 73gAA g BDO, 112.5g BDO and 0.17g tetrabutyl titanate are put into a three-neck flask, fully stirred, the temperature is controlled at 180 ℃, the reaction is carried out for 2 hours, then 7.1g glycidyl methacrylate is added into the three-neck flask, the reaction is continued for 1 hour, the cooling and the drying are carried out, and the end-capped PBAT resin A with the molecular weight of 40000 is obtained.
b. 400g of end-capped 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 screw rotation speed is 300rpm, and the screw temperature is set as from the feed opening to the machine head section: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃; obtaining PLA modified resin B.
(2) PLA foaming material preparation
PLA modified resin B, PLA resin and talcum powder were fed into a twin screw extruder with reference to the raw material amounts of Table 3, and extrusion conditions were: the screw rotation speed is 300rpm, and the screw temperature is set as from the feed opening to the machine head section: 170 ℃, 175 ℃, 185 ℃, and the like 185 ℃, 190 ℃,200 ℃; cooling the extruded material in an extruder water tank, granulating, 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) PLA foam bead preparation
Adding PLA foaming material into a foaming autoclave, vacuumizing to remove water, injecting supercritical CO by an injection pump 2 The mixture was pressurized at 7.5MPa and warmed to 100deg.C, saturated for 60min, and the pressure was rapidly released and the PLA bead foam was collected.
Example 3
(1) PLA-modified resin C:
a. 74.7g of PTA, 80.3g of gAA, 126g of BDO and 0.17g of tetrabutyl titanate are put into a three-neck flask, fully stirred, the temperature is controlled at 190 ℃, the reaction is carried out for 2.5 hours, then 7.1g of glycidyl methacrylate is added into the three-neck flask, the reaction is continued for 1.5 hours, the cooling and the drying are carried out, and the hydroxy glycidyl methacrylate end-capped oligomeric PBAT with the molecular weight of 25000 is obtained.
b. 600g of end-capped PBAT resin C, 1000g of 070D and 1.8g of methyl ethyl ketone peroxide are taken and put into a double-screw extruder, and extrusion conditions are as follows: the screw rotation speed is 500rpm, and the screw temperature is set as from the feed opening to the machine head section: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃,200 ℃, 210 ℃; obtaining PLA modified resin C.
(2) PLA foaming material preparation
PLA modified resin C, PLLA and talcum powder were fed into a twin screw extruder with reference to the amounts of raw materials in Table 3, the extrusion conditions were: the screw rotation speed is 500rpm, and the screw temperature is set as from the feed opening to the machine head section: 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃; cooling the extruded material in an extruder water tank, granulating, 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) PLA foam bead preparation
Adding PLA foaming material into a foaming autoclave, vacuumizing to remove water, injecting supercritical CO by an injection pump 2 The mixture was pressurized at 9MPa and warmed to 115℃and after 80min of saturation, the pressure was rapidly released and the PLA bead foam was collected.
Comparative example 1
This comparative example directly uses commercially available PBAT in place of PLA modifier and PLA expanded beads were prepared as in example 2, except that the formulation in table 3 was different.
Comparative example 2
This comparative example directly uses commercial PBAT and PDLA in place of PLA modifier 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 PLA modifier and PLA expanded beads were prepared as in example 2, except that the formulation composition in table 3 was different.
The results of the performance test of the foamed sheets obtained in examples 1-3 and comparative examples 1-2 are shown in Table 4.
TABLE 3 raw materials and amounts (Kg) in examples 1-3 (S1-S3) and comparative examples 1-3 (D1-D3)
| Raw materials | 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 Performance test of the products 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, as commercial PBAT was added directly, there was no faster nucleation, the average cell size was large, and the crystallinity was low. As can be seen from comparative example 2 and examples 1-3, as commercial PBAT and PDLA were added directly, phase separation easily occurred due to poor compatibility of PLA and PBAT, and the foamed PLA foam cells were not uniform after foaming. It can be seen from comparative example 3 and examples 1-3 that no PLA modifier was added, no faster nucleation was achieved, the average cell size was large and the cell strength was low. Examples 1-3 show that the prepared PLA foaming beads have high foaming multiplying power and uniform foam holes. Supercritical CO 2 Under the condition of being used as a foaming agent, the foaming multiplying power can reach 30 times, the foam holes are uniform, and the foaming agent has high market application value.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. A polylactic acid foam material comprising the following composition:
55-98 parts by mass of PLA resin,
2-40 parts by mass of PLA modifier,
0.2 to 5 parts by mass of inorganic filler,
the PLA modifier is of a PBAT-g-PDLA structure; 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 capping agent glycidyl methacrylate, reacting, and capping the PBAT resin to obtain capped PBAT resin;
(3) Extruding the end-capped PBAT resin and PDLA in a double-screw extruder under the action of an initiator to obtain a PLA modifier; in the step (2), the molar ratio of the 1, 4-butanediol to the glycidyl methacrylate is 30:1-10:1, a step of; in the step (3), PDLA: end-capped PBAT resin: the mass ratio of the initiator is 1000: (100-800): (0.2-2).
2. The polylactic acid foam material according to claim 1, comprising the following composition:
86-95 parts by mass of PLA resin,
5-20 parts by mass of PLA modifier,
0.5-4 parts by mass of inorganic filler.
3. The polylactic acid foam material according to claim 1, wherein the PLA resin has a melt index of 2-8g/10min, and the test condition is 190 ℃,2.16kg.
4. The polylactic acid foam material according to claim 1, wherein the PLA resin is selected from one or more of LX575, LX175, LX530 of Total cobion company, 4032D, 8052D, 2002D of nature, revole 110, revole 190, revole 101 of Zhejiang, FY801, FY802, FY804 of angfeng company, LX575, LX175 of Total cobion company.
5. The polylactic acid foam material according to claim 1, wherein the inorganic filler is one or more of talc, mica and montmorillonite.
6. The polylactic acid foam material according to any one of claims 1 to 5, wherein the inorganic filler has a mesh number of 1000 to 10000 mesh.
7. The polylactic acid foam material according to claim 1, wherein the PLA modifier is prepared by free radical reaction of a blocked PBAT resin and PDLA under the action of an initiator.
8. The polylactic acid foam material according to claim 1, wherein in the step (3), PDLA: end-capped PBAT resin: the mass ratio of the initiator is 1000: (200-600): (0.5-1.8).
9. A method for preparing the polylactic acid foam 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: the polylactic acid foaming material according to any one of claims 1 to 8 is placed in a high-pressure reaction kettle, the foaming agent is pressurized to 6 to 9MPa, then heated to 80 to 120 ℃, saturated for 60 to 90min, and decompressed and cooled.
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