CN115505242B - Full-biodegradable foam material and preparation method and application thereof - Google Patents
Full-biodegradable foam material and preparation method and application thereof Download PDFInfo
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- CN115505242B CN115505242B CN202110635457.XA CN202110635457A CN115505242B CN 115505242 B CN115505242 B CN 115505242B CN 202110635457 A CN202110635457 A CN 202110635457A CN 115505242 B CN115505242 B CN 115505242B
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- 239000006261 foam material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005187 foaming Methods 0.000 claims abstract description 61
- -1 polybutylene adipate Polymers 0.000 claims abstract description 32
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 24
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 24
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 14
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003623 enhancer Substances 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims 1
- 239000005022 packaging material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000006835 compression Effects 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 10
- 238000006065 biodegradation reaction Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 229920005839 ecoflex® Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-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
- 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
- C08J9/0061—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
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2451/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of degradable high polymer materials, and discloses a full-biodegradable foaming material, a preparation method and application thereof, wherein the method comprises the following steps: 10-35 parts by weight of polyglycolic acid, 65-90 parts by weight of polybutylene adipate, 0.2-2.5 parts by weight of maleic anhydride graft polymer, 0.5-3 parts by weight of melt reinforcing agent and 0.1-1.5 parts by weight of antioxidant are mixed, and then extrusion supercritical gas foaming or intermittent supercritical gas foaming is carried out, so that the full-biodegradation foaming material is obtained. The preparation method of the full-biodegradable foam material provided by the invention is simple to operate and low in production cost, and the obtained full-biodegradable foam material has the advantages of small shrinkage, large compression recovery rate and good rebound resilience.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a full-biodegradation foam material and a preparation method and application thereof.
Background
Most of the foaming plastics on the market at present are petroleum-based products such as polyvinyl chloride, polystyrene, polyethylene, polypropylene and the like, and the products have the advantages of low density, good performance and low price, but the biggest problem is difficult recovery and degradation, and are the main sources of white pollution in the environment.
In the new edition of "plastic restriction" in 2020, in the opinion about further strengthening plastic pollution control, non-degradable plastic bags, disposable plastic tableware, express plastic packages and the like are all included in the scope of prohibition and restriction of use, and production and sales of disposable foamed plastic tableware are prohibited at the end of 2020.
In order to respond to the national policy, developing a fully biodegradable foam material to replace most of the currently used foam plastics which are not degradable or difficult to recycle is an important way to solve the problem of white pollution. The polybutylene adipate is a full-biodegradable polymer, has the advantages of good impact property, easiness in processing and full degradation, and has a good application prospect in the field of buffer packaging. However, the polybutylene adipate foaming material has the problems of low modulus, poor cell supporting force, easy collapse of cells, high shrinkage, low compression recovery rate, poor rebound resilience and easy shrinkage of the foaming skin.
Disclosure of Invention
The invention aims to solve the problems of large shrinkage, small compression recovery rate and poor rebound resilience of a polybutylene adipate foaming material in the prior art, and provides a full-biodegradation foaming material and a preparation method and application thereof. The preparation method of the full-biodegradable foam material provided by the invention is simple to operate and low in production cost, and the obtained full-biodegradable foam material has the advantages of small shrinkage, large compression recovery rate and good rebound resilience.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a fully biodegradable foam material, the method comprising: 10-35 parts by weight of polyglycolic acid, 65-90 parts by weight of polybutylene adipate, 0.2-2.5 parts by weight of maleic anhydride graft polymer, 0.5-3 parts by weight of melt reinforcing agent and 0.1-1.5 parts by weight of antioxidant are mixed, and then extrusion supercritical gas foaming or intermittent supercritical gas foaming is carried out, so that the full-biodegradation foaming material is obtained.
The second aspect of the invention provides a full-biodegradable foam material prepared by the preparation method provided by the first aspect of the invention.
The third aspect of the invention provides an application of the full-biodegradable foam material provided by the second aspect of the invention in the field of buffer packaging.
Through the technical scheme, the full-biodegradable foaming material, the preparation method and the application of the full-biodegradable foaming material provided by the invention can obtain the following beneficial effects:
1) The preparation method of the full-biodegradable foam material provided by the invention is simple to operate, low in production cost and suitable for industrial popularization;
2) The fully biodegradable foaming material provided by the invention utilizes the synergistic effect among the polyglycolic acid, the polybutylene adipate, the maleic anhydride grafted polymer, the melt reinforcing agent and the antioxidant, so that the cell supporting force of the fully biodegradable foaming material obtained when the polybutylene adipate is taken as a main foaming raw material is improved, the compression recovery rate of the obtained fully biodegradable foaming material is increased, the shrinkage rate of the fully biodegradable foaming material is reduced, and the elasticity performance of the fully biodegradable foaming material is improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a preparation method of a full-biodegradable foam material, which comprises the following steps: 10-35 parts by weight of polyglycolic acid, 65-90 parts by weight of polybutylene adipate, 0.2-2.5 parts by weight of maleic anhydride graft polymer, 0.5-3 parts by weight of melt reinforcing agent and 0.1-1.5 parts by weight of antioxidant are mixed, and then extrusion supercritical gas foaming or intermittent supercritical gas foaming is carried out, so that the full-biodegradation foaming material is obtained.
In some embodiments of the present invention, preferably, the method includes: mixing 20-30 parts by weight of polyglycolic acid, 70-80 parts by weight of polybutylene adipate, 0.5-2 parts by weight of maleic anhydride graft polymer, 1-2 parts by weight of melt reinforcing agent and 0.5-1 part by weight of antioxidant, and then extruding supercritical gas foaming or intermittent supercritical gas foaming to obtain the full-biodegradable foaming material.
The inventor discovers that the proportion of polyglycolic acid, polybutylene adipate, maleic anhydride grafted polymer, melt reinforcing agent and antioxidant is controlled within the range, and the components are foamed by utilizing supercritical gas, so that the cell supporting force of the fully biodegradable foaming material obtained when polybutylene adipate is taken as a main foaming raw material can be improved, the compression recovery rate of the fully biodegradable foaming material is increased, the shrinkage rate of the fully biodegradable foaming material is reduced, and the elasticity performance of the fully biodegradable foaming material is improved.
In some embodiments of the present invention, preferably, the polyglycolic acid (PGA) has a weight average molecular weight of 50000 to 300000, preferably 100000 to 250000.
In some embodiments of the invention, preferably, the polyglycolic acid has a melt index of 20 to 40g/10min, preferably 25 to 30g/10min, at 240℃and under a 2.16kg load. Among them, the melt index of polyglycolic acid was measured by GB/T3682.2000.
In some embodiments of the invention, the polybutylene adipate (PBAT) preferably has a melt index of 2 to 30g/10min, preferably 20 to 30g/10min, at 190℃and under a load of 2.16 kg. Among them, polybutylene adipate was tested for melt index using GB/T3682.2000.
In some embodiments of the present invention, preferably, the maleic anhydride graft polymer is at least one selected from the group consisting of maleic anhydride graft polyethylene, maleic anhydride graft POE, and maleic anhydride graft polypropylene; preferably, the grafting ratio of the maleic anhydride-grafted polymer is 0.2 to 5 wt%. The weight average molecular weight of the maleic anhydride graft polymer is not particularly limited, and maleic anhydride graft polymers of common specifications on the market can be used in the invention.
In some embodiments of the present invention, preferably, the melt enhancer is a copolymer containing glycidyl methacrylate groups and/or a polyisocyanate compound, preferably a copolymer containing glycidyl methacrylate groups and a polyisocyanate compound, wherein the mass ratio of the copolymer containing glycidyl methacrylate groups to the polyisocyanate compound is 1:0.5 to 5.5, preferably 1:1 to 3.
The invention selects the copolymer containing glycidyl methacrylate groups and the poly-isonitrile acid ester compound as melt reinforcing agents, thereby effectively enhancing the melt strength of the polybutylene adipate and the polyglycolic acid and further improving the shrinkage and the elastic recovery of the obtained foaming material.
In some embodiments of the present invention, preferably, the copolymer has a glycidyl methacrylate group content of 6 to 16wt% and a weight average molecular weight of 5500 to 7500; further preferably, the content of glycidyl methacrylate groups in the copolymer is 8 to 12wt%, and the weight average molecular weight of the copolymer is 6000 to 7000;
further preferably, the copolymer is selected from at least one of styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, POE elastomer-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate copolymer; more preferably, the copolymer is selected from styrene-glycidyl methacrylate copolymer and/or ethylene-methyl acrylate-glycidyl methacrylate copolymer. Among these, the copolymers of the present invention are all common commercial products.
In some embodiments of the present invention, preferably, the polyisocyanate compound is at least one selected from toluene-2, 4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, and polyisocyanate, and preferably is polyisocyanate. Wherein the polyisocyanate has a viscosity of 100 to 300mpa.s, preferably 150 to 250mpa.s, at 25 ℃; the polyisocyanate has an NCO content of 28.5 to 35% by weight, preferably 30.2 to 32% by weight; the functionality of the polyisocyanates is from 2.4 to 3, preferably from 2.6 to 2.7.
In some embodiments of the present invention, preferably, at least one selected from the group consisting of antioxidant 168, antioxidant 1010 and antioxidant 9228, and more preferably, antioxidant 1010.
In some embodiments of the invention, preferably, the blend obtained by mixing polyglycolic acid, polybutylene adipate, maleic anhydride grafted polymer, melt enhancer, and antioxidant has a loss factor of less than 3, preferably less than 2; the melt draw ratio is greater than 2, preferably greater than 3.
In some embodiments of the present invention, preferably, the polyglycolic acid, polybutylene adipate, maleic anhydride graft polymer, melt enhancer, and antioxidant are dried prior to mixing, the drying conditions comprising: the drying temperature is 50-100deg.C, more preferably 60-80deg.C; the drying time is 2 to 12 hours, more preferably 5 to 10 hours.
In some embodiments of the present invention, preferably, the supercritical gas is carbon dioxide and/or nitrogen, and more preferably, carbon dioxide.
In some embodiments of the present invention, preferably, the extrusion supercritical gas foaming is foaming by using supercritical gas in the melt blending process after mixing, wherein the extrusion supercritical gas foaming is performed in a twin screw extruder, and the conditions of extrusion supercritical gas foaming include: the temperature of the feeding section is 180-210 ℃, the temperature of the plasticizing section is 200-230 ℃, the temperature of the homogenizing section is 170-230 ℃, and the temperature of the extrusion die head is 110-160 ℃; the extrusion die pressure is 5-25Mpa.
In some embodiments of the present invention, preferably, the intermittent supercritical gas is foamed, and then mixed, and melt blended to obtain a granular product, and then the granular product is pressed into a tablet-shaped product, and then foamed by using the supercritical gas.
Wherein the conditions of melt blending include: the temperature is 220-250 ℃, preferably 225-235 ℃; the rotation speed is 50-120r/min, preferably 70-100r/min.
Wherein the conditions for supercritical gas foaming include: the foaming temperature is 110-160 ℃, preferably 120-140 ℃; the foaming pressure is 5-20MPa, preferably 10-20MPa; the foaming time is 1-3h, preferably 1.5-2.5h.
The melt blending is performed in a double-screw extruder, the tabletting is performed in a tablet press, the sheet-shaped product is subjected to supercritical gas foaming in a reaction kettle, and after the foaming is finished, the pressure is quickly released to normal pressure, so that the full-biodegradable foaming material is obtained.
The second aspect of the invention provides a full-biodegradable foam material prepared by the preparation method of the first aspect of the invention.
In some embodiments of the present invention, preferably, the compression recovery rate of the fully biodegradable foam material is 92-98%, and more preferably 96-97%; shrinkage is 6-18%, more preferably 7-12%; the elongation at break is 50 to 99%, more preferably 82 to 98%.
In some embodiments of the present invention, preferably, the density of the fully biodegradable foam material is 0.1-0.17g/cm 3 Further preferably 0.1 to 0.12g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The foaming ratio is 8 to 15, more preferably 10 to 13; the average pore diameter is 40 to 80. Mu.m, more preferably 45 to 65. Mu.m.
The third aspect of the invention provides an application of the full-biodegradable foam material in the field of buffer packaging.
The present invention will be described in detail by examples. In the following examples, polyglycolic acid was purchased from Shanghai Pu Jing and had a weight average molecular weight of 100000, a melt index of 28g/10min at 240℃and a load of 2.16 kg.
Polybutylene adipate was a melt index of 30g/10min at 190℃and a load of 2.16kg, purchased from Basff, of Ecoflex F blend C.
Maleic anhydride grafted POE was purchased from dow chemical GR216 (grafting 0.5 wt% to 1.0 wt%).
Polyisocyanates (PMDI), PM200 (viscosity 150-250 mPas at 25 ℃ C., -NCO content 30.2-32% by weight, functionality 2.6-2.7) from Van der Waals chemical production.
Styrene-glycidyl methacrylate copolymer: pasteur ADR-4468 (glycidyl methacrylate group GMA content 10% by weight, weight average molecular weight about 6680).
The antioxidant is 1010.
Wherein, the loss factor testing method in the examples and the comparative examples adopts a rotary rheometer to carry out sweep frequency test of 0.1-100rad/s; the elongational viscosity and the melt stretch ratio test method are carried out by adopting a melt stretcher at 230 ℃ and 0.1 rad/s; test instrument universal stretcher of compression recovery rate, test condition: and (3) compressing the foaming sample with the thickness of a1 by 50% along the thickness direction for 10min, releasing the pressure, placing the sample in a natural state for recovering for 10min, measuring the thickness of a2, and calculating the thickness of a2/a1 by 100% to obtain the compression recovery rate. The shrinkage test method in the examples and the comparative examples comprises measuring the expansion ratio b1 after foaming and the expansion ratio b2 after 12 hours of standing, and calculating (1-b 2/b 1) by 100% to obtain the shrinkage; the average foam density of the foam material is measured according to GB/T6344-1996; the pore diameter of the foam material is measured by a microscopic measuring method; elongation at break was measured according to GB/T1033.2-2008.
Example 1
Firstly, respectively drying polyglycolic acid, polybutylene adipate, a maleic anhydride graft polymer, a melt reinforcing agent and an antioxidant at 80 ℃ for 8 hours, then uniformly mixing, putting into a double-screw extruder, firstly carrying out melt blending at 235 ℃ and 100r/min to obtain a granular product, pressing the granular product into a sheet-shaped product with the thickness of 2mm, putting into an intermittent reaction kettle, introducing supercritical carbon dioxide, maintaining the pressure at 128 ℃ and 20MPa for 1.5 hours, foaming, and rapidly releasing pressure to normal pressure after the foaming is finished to obtain the full-biodegradable foaming material.
Among them, the types and amounts of polyglycolic acid, polybutylene adipate, maleic anhydride graft polymer, melt enhancer and antioxidant in example 1 are shown in Table 1, the performance parameters of the melt-blended blend are shown in Table 2, and the test results are shown in Table 3.
Examples 2 to 5
Similar to example 1, the difference is that: the types and amounts of polyglycolic acid, polybutylene adipate, maleic anhydride graft polymer, melt enhancer, and antioxidant used in examples 2-5 are shown in Table 1, the performance parameters of the melt-blended blends are shown in Table 2, and the test results are shown in Table 3.
Comparative examples 1 to 3
Similar to example 1, the difference is that: the types and amounts of polyglycolic acid, polybutylene adipate, melt-reinforcing agent and antioxidant used in comparative examples 1 to 3 are shown in Table 1, the performance parameters of the melt-blended blends are shown in Table 2, and the test results are shown in Table 3.
TABLE 1
TABLE 2
| Loss factor | Melt draw ratio | |
| Example 1 | 1.3 | Greater than 3 |
| Example 2 | 1.6 | Greater than 3 |
| Example 3 | 2.3 | Greater than 3 |
| Example 4 | 1.9 | 2.5 |
| Example 5 | 2.0 | 2.7 |
| Comparative example 1 | 4 | Greater than 3 |
| Comparative example 2 | 3.5 | 1.5 |
| Comparative example 3 | 3.2 | 1.7 |
TABLE 3 Table 3
As can be seen from the data in Table 1, the preparation method provided by the invention improves the cell supporting force of the fully biodegradable foam material obtained when the polybutylene adipate is taken as the main foaming raw material by utilizing the synergistic effect among the polyglycolic acid, the polybutylene adipate, the maleic anhydride grafted polymer, the melt reinforcing agent and the antioxidant, increases the compression recovery rate of the fully biodegradable foam material, reduces the shrinkage rate of the fully biodegradable foam material, and improves the elastic performance of the fully biodegradable foam material.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (16)
1. A method for preparing a fully biodegradable foam material, the method comprising:
10-35 parts by weight of polyglycolic acid, 65-90 parts by weight of polybutylene adipate, 0.2-2.5 parts by weight of maleic anhydride graft polymer, 0.5-3 parts by weight of melt reinforcing agent and 0.1-1.5 parts by weight of antioxidant are mixed and then extruded to form supercritical gas foam or intermittent supercritical gas foam, so as to obtain a full-biodegradable foam material; wherein the melt reinforcing agent is a copolymer containing glycidyl methacrylate groups and/or a polyisocyanate compound.
2. The process according to claim 1, wherein the polyglycolic acid has a weight-average molecular weight of 50000 to 300000;
and/or the melt index of the polyglycolic acid at 240 ℃ and 2.16kg load is 20-40g/10min.
3. The production method according to claim 2, wherein the polyglycolic acid has a weight-average molecular weight of 100000 to 250000;
and/or the polyglycolic acid has a melt index of 25-30g/10min at 240 ℃ and a load of 2.16 kg.
4. The process according to claim 1 or 2, wherein the polybutylene adipate has a melt index of 2-30g/10min at 190 ℃ and under a load of 2.16 kg.
5. The process according to claim 4, wherein the polybutylene adipate has a melt index of 5 to 20g/10min at 190℃and under a load of 2.16. 2.16 kg.
6. The production method according to claim 1, wherein the maleic anhydride-grafted polymer is at least one selected from the group consisting of maleic anhydride-grafted polyethylene, maleic anhydride-grafted POE, and maleic anhydride-grafted polypropylene.
7. The process according to claim 1, wherein the maleic anhydride-grafted polymer has a grafting ratio of 0.2 to 5% by weight and a weight average molecular weight of 20000 to 130000.
8. The preparation method according to claim 1, wherein the melt enhancer is a copolymer containing glycidyl methacrylate groups and a polyisocyanate compound, and wherein the mass ratio of the copolymer containing glycidyl methacrylate groups to the polyisocyanate compound is 1:0.5-5.5.
9. The process according to claim 8, wherein the mass ratio of the copolymer containing glycidyl methacrylate groups to the polyisocyanate compound is 1:1 to 3.
10. The preparation method according to claim 1, wherein the antioxidant is at least one selected from the group consisting of antioxidant 168, antioxidant 1010 and antioxidant 9228.
11. The method of claim 10, wherein the antioxidant is antioxidant 1010.
12. The production method according to claim 1, wherein the extrusion supercritical gas foaming is foaming with supercritical gas in the melt blending process after mixing, wherein the conditions of extrusion supercritical gas foaming include: the temperature of the feeding section is 180-210 ℃, the temperature of the plasticizing section is 200-230 ℃, the temperature of the homogenizing section is 170-230 ℃, and the temperature of the extrusion die head is 110-160 ℃; the extrusion die head pressure is 5-25MPa.
13. The preparation method according to claim 1, wherein the intermittent supercritical gas foaming is performed by mixing, then melt blending to obtain a granular product, pressing the granular product into a sheet-like product, and then foaming by supercritical gas;
wherein the conditions of melt blending include: the temperature is 220-250 ℃ and the rotating speed is 50-120r/min;
wherein the conditions under which the supercritical gas is foamed include: the foaming temperature is 110-160 ℃, the foaming pressure is 5-25MPa, and the foaming time is 1-3h.
14. The method of manufacture of claim 13, wherein the melt blending conditions comprise: the temperature is 225-235 ℃ and the rotating speed is 70-100r/min;
wherein the conditions under which the supercritical gas is foamed include: the foaming temperature is 120-140 ℃, the foaming pressure is 10-20MPa, and the foaming time is 1.5-2.5h.
15. A fully biodegradable foam material prepared by the preparation method of any one of claims 1 to 14.
16. Use of the fully biodegradable foam material according to claim 15 in cushioning packaging material.
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| TW201209087A (en) * | 2010-08-25 | 2012-03-01 | Jin-Fu Chen | Biomass composite material composition and foaming method thereof |
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| KR20160093802A (en) * | 2015-01-29 | 2016-08-09 | (주)엘지하우시스 | Biodegradable bead foam and the preparation method for the same |
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