CN116535838A - Degradable biomass composite foaming material and preparation method and application thereof - Google Patents
Degradable biomass composite foaming material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116535838A CN116535838A CN202310696259.3A CN202310696259A CN116535838A CN 116535838 A CN116535838 A CN 116535838A CN 202310696259 A CN202310696259 A CN 202310696259A CN 116535838 A CN116535838 A CN 116535838A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- foaming
- coupling agent
- straw fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005187 foaming Methods 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000002028 Biomass Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000010902 straw Substances 0.000 claims abstract description 78
- 239000000835 fiber Substances 0.000 claims abstract description 76
- 239000011256 inorganic filler Substances 0.000 claims abstract description 37
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000004626 polylactic acid Substances 0.000 claims abstract description 24
- 229920005570 flexible polymer Polymers 0.000 claims abstract description 23
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- 239000003365 glass fiber Substances 0.000 claims description 28
- -1 peroxy hexane Chemical compound 0.000 claims description 27
- 244000068988 Glycine max Species 0.000 claims description 16
- 235000010469 Glycine max Nutrition 0.000 claims description 16
- 239000006261 foam material Substances 0.000 claims description 15
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 14
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 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 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- NQZRDXDTNFGVMK-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCC(=O)OCCCCO1 NQZRDXDTNFGVMK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- 240000000111 Saccharum officinarum Species 0.000 claims description 3
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 description 23
- 239000008187 granular material Substances 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004088 foaming agent Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 6
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229920002961 polybutylene succinate Polymers 0.000 description 5
- 239000004631 polybutylene succinate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QFXQWGIEIVHAIK-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione 1,6-dioxecane-2,5-dione Chemical compound C1(C2=CC=C(C(=O)OCCCCO1)C=C2)=O.C2(CCC(=O)OCCCCO2)=O QFXQWGIEIVHAIK-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 238000009264 composting Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/009—Use of pretreated 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- 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
- 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
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/14—Homopolymers or copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of foaming materials, and particularly relates to a degradable biomass composite foaming material, and a preparation method and application thereof. The degradable biomass composite foaming material provided by the invention is prepared by foaming after melt blending of raw materials, and the raw materials comprise the following components in parts by weight: 50-80 parts of polylactic acid, 20-50 parts of flexible polymer, 50-80 parts of surface modified straw fiber, 10-20 parts of surface modified inorganic filler, 0.1-0.3 part of cross-linking agent, 1-2.5 parts of compatibilizer, 5-10 parts of plasticizer, 0.5-2 parts of lubricant and 0.1-1 part of antioxidant. According to the invention, the component composition of the foaming material is optimally designed, so that the production cost of the foaming material is obviously reduced, and the comprehensive performance of the foaming material is improved.
Description
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to a degradable biomass composite foaming material, and a preparation method and application thereof.
Background
At present, plastic products are spread over the production and life of people, the annual yield of plastic products is statistically over 3.6 hundred million tons worldwide, and most of raw materials are derived from fossil resources such as petroleum, coal and the like. With the increasing exhaustion of petrochemical resources and the increasing evolution of "white pollution", energy and environmental problems are the subjects of sustainable development in society. In recent years, biodegradable materials are increasingly valued for their biodegradability, wide sources, non-toxicity and other advantages.
With the rapid development of the quick-release industry and the logistics packaging industry, the demand of the market for cushioning packaging materials is increasing. The biodegradable foaming material is a novel environment-friendly packaging material, has the performances of biodegradability, good buffering performance, light weight, heat preservation, moisture resistance, corrosion resistance and the like, can reduce the use amount of plastics, reduce carbon emission and reduce cost to a certain extent, is widely applied to vehicle transportation and express packaging in the logistics industry, and is expected to become one of the most important buffering and protecting materials for transportation packaging.
At present, most foaming materials are prepared from petroleum-based polymers, are difficult to degrade and recycle, and increase white pollution after being abandoned, so that energy conservation and environmental pollution relief are not facilitated. The existing biodegradable foaming material contains non-biodegradable polymer and cannot be completely biodegradable; or the production cost is relatively high, which is not beneficial to the application and popularization of the biodegradable material.
Disclosure of Invention
In view of the above, the invention aims to provide a degradable biomass composite foaming material, a preparation method and application thereof.
The invention provides a degradable biomass composite foaming material which is prepared by foaming after melt blending of raw materials, wherein the raw materials comprise the following components in parts by weight:
the flexible polymer is one or more of poly (butylene succinate/terephthalate), poly (butylene succinate-terephthalate), poly (butylene succinate/adipate) and polycaprolactone;
the surface modified straw fiber is a coupling agent modified straw fiber, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent;
the surface modified inorganic filler is a coupling agent modified inorganic filler, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent;
the cross-linking agent is one or more of dicumyl peroxide, dibenzoyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and peroxy hexane;
the compatibilizer is styrene-acrylic acid-glycidyl methacrylate copolymer.
Preferably, the total weight part of the polylactic acid and the flexible polymer in the raw material is 100 parts.
Preferably, the straw fiber in the coupling agent modified straw fiber is one or more of straw fiber, wheat straw fiber, sugarcane straw fiber, soybean straw fiber and corn straw fiber.
Preferably, the inorganic filler in the coupling agent modified inorganic filler is one or more of talcum powder, calcium carbonate, white carbon black, glass fiber, basalt fiber, montmorillonite and wollastonite.
Preferably, the plasticizer is epoxidized soybean oil and/or citrate.
Preferably, the lubricant is pentaerythritol stearate and/or ethylene bisstearamide.
Preferably, the antioxidant is antioxidant 1076 and/or antioxidant 168.
The invention provides a preparation method of the degradable biomass composite foaming material, which comprises the following steps:
a) Melt blending polylactic acid, a flexible polymer, surface modified straw fiber, surface modified inorganic filler, a cross-linking agent, a compatibilizer, a plasticizer, a lubricant and an antioxidant to obtain a material to be foamed;
b) And foaming the material to be foamed to obtain the degradable biomass composite foaming material.
Preferably, in step b), the foaming mode is physical foaming; the foaming temperature is 60-180 ℃; the foaming pressure is 5-20 MPa; the foaming pressurization time is 1-5 h; the pressure release time of the foaming is 0.1-20 s.
The invention provides a degradable biomass composite foaming sheet material, which is prepared from the degradable biomass composite foaming material in the technical scheme.
Compared with the prior art, the invention provides a degradable biomass composite foaming material, and a preparation method and application thereof. The degradable biomass composite foaming material provided by the invention is prepared by foaming after melt blending of raw materials, and the raw materials comprise the following components in parts by weight: 50-80 parts of polylactic acid, 20-50 parts of flexible polymer, 50-80 parts of surface modified straw fiber, 10-20 parts of surface modified inorganic filler, 0.1-0.3 part of cross-linking agent, 1-2.5 parts of compatibilizer, 5-10 parts of plasticizer, 0.5-2 parts of lubricant and 0.1-1 part of antioxidant; the flexible polymer is one or more of poly (butylene succinate/terephthalate), poly (butylene succinate-terephthalate), poly (butylene succinate/adipate) and polycaprolactone; the surface modified straw fiber is a coupling agent modified straw fiber, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent; the surface modified inorganic filler is a coupling agent modified inorganic filler, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent; the cross-linking agent is one or more of dicumyl peroxide, dibenzoyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and peroxy hexane; the compatibilizer is styrene-acrylic acid-glycidyl methacrylate copolymer. According to the invention, the component composition of the foaming material is optimally designed, so that the production cost of the foaming material is obviously reduced, the comprehensive performance of the foaming material is improved, and in particular: 1) Polylactic acid is used as a foaming matrix material, and a biodegradable flexible polymer is added to make up for the shortcoming of brittleness of the polylactic acid; 2) Natural easily biodegradable straw fibers are used as a cost-reducing additive; 3) Inorganic filler is added to enhance the foaming mechanical property and serve as heterogeneous nucleating agent to promote the nucleation of cells; 4) Surface modification is carried out on the straw fibers and the inorganic filler, so that the interfacial binding force between the straw fibers and the inorganic filler and the polymer matrix is enhanced, the dispersibility of the straw fibers and the inorganic filler in the matrix is improved, and the mechanical property of the foaming material is obviously improved; 5) Adding a cross-linking agent to generate a cross-linking structure on a molecular chain, so that the melt strength is improved, and the dimensional stability after foaming is increased; 6) And the compatibilizer is added, so that the compatibility among polymers is effectively improved. The degradable biomass composite foaming material provided by the invention has good foaming performance and comprehensive mechanical property, the preparation process is simple and easy to control, the production cost is low, the production efficiency is high, and the degradable biomass composite foaming material is suitable for large-scale production.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a degradable biomass composite foaming material which is prepared by foaming after melt blending of raw materials, wherein the raw materials comprise the following components in parts by weight:
in the composite foaming material provided by the invention, the weight average molecular weight of the polylactic acid (PLA) is preferably 15-40 ten thousand, and can be 15 ten thousand, 16 ten thousand, 17 ten thousand, 18 ten thousand, 19 ten thousand, 20 ten thousand, 21 ten thousand, 22 ten thousand, 23 ten thousand, 24 ten thousand, 25 ten thousand, 26 ten thousand, 27 ten thousand, 28 ten thousand, 29 ten thousand, 30 ten thousand, 31 ten thousand, 32 ten thousand, 33 ten thousand, 34 ten thousand, 35 ten thousand, 36 ten thousand, 37 ten thousand, 38 ten thousand, 39 ten thousand or 40 ten thousand.
In the composite foam material provided by the invention, the content of the polylactic acid in the raw material may specifically be 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight or 80 parts by weight.
In the composite foam material provided by the invention, the flexible polymer is one or more of poly (butylene succinate)/terephthalate (PBAT), poly (butylene succinate-butylene terephthalate) (PBST), poly (butylene succinate) (PBS), poly (butylene succinate/butylene adipate) (PBSA) and Polycaprolactone (PCL), preferably poly (butylene succinate-butylene terephthalate), polycaprolactone and polybutylene succinate, and the mass ratio of the poly (butylene succinate-butylene terephthalate), polycaprolactone and polybutylene succinate is preferably 20 (5-30): (5-30), more preferably 20 (10-20): (10-20), and most preferably 20:15:15; the molar ratio of the polybutylene succinate segment to the polybutylene terephthalate segment in the poly (butylene succinate-butylene terephthalate) is preferably (90:10) - (10:90), more preferably (70:30) - (30:70), most preferably (60:40) - (40:60), and particularly may be 50:50; the weight average molecular weight of the flexible polymer is preferably 20-50 ten thousand, and can be 20 ten thousand, 21 ten thousand, 22 ten thousand, 23 ten thousand, 24 ten thousand, 25 ten thousand, 26 ten thousand, 27 ten thousand, 28 ten thousand, 29 ten thousand, 30 ten thousand, 31 ten thousand, 32 ten thousand, 33 ten thousand, 34 ten thousand, 35 ten thousand, 36 ten thousand, 37 ten thousand, 38 ten thousand, 39 ten thousand, 40 ten thousand, 41 ten thousand, 42 ten thousand, 43 ten thousand, 44 ten thousand, 45 ten thousand, 46 ten thousand, 47 ten thousand, 48 ten thousand, 49 ten thousand or 50 ten thousand.
In the composite foam material provided by the invention, the content of the flexible polymer in the raw material substance can be specifically 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight or 50 parts by weight.
In the composite foam material provided by the invention, the total content of the polylactic acid and the flexible polymer in the raw material is preferably 100 parts by weight.
In the composite foaming material provided by the invention, the surface modified straw fiber is a coupling agent modified straw fiber, and is prepared by mixing the straw fiber and the coupling agent; wherein the straw fiber is preferably one or more of straw fiber, wheat straw fiber, sugarcane straw fiber, soybean straw fiber and corn straw fiber, more preferably soybean straw fiber and/or straw fiber, and the mass ratio of the soybean straw fiber to the straw fiber is preferably 3 (1-5), more preferably 3:2; the particle size of the straw fiber is preferably less than or equal to 1000 mu m, more preferably less than or equal to 800 mu m; the water content of the straw fiber is preferably less than or equal to 2%, more preferably less than or equal to 1%; the coupling agent is preferably one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent, and more preferably is maleic anhydride or an aluminum-titanium composite coupling agent; the mass ratio of the straw fiber to the coupling agent is preferably 100 (1-10), and can be specifically 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9 and 100:10.
In the composite foam material provided by the invention, the surface modified straw fiber is preferably prepared according to the following steps: mixing the pretreated straw fiber with a coupling agent to obtain a surface modified straw fiber; wherein, the specific process of pretreatment preferably comprises: crushing, sieving and drying the straw fiber raw material; the mixing temperature is preferably 80-100 ℃, and can be specifically 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃; the mixing time is preferably 10-60 min, and can be specifically 10min, 20min, 30min, 40min, 50min or 60min.
In the composite foam material provided by the invention, the content of the surface-modified straw fiber in the raw material substance can be specifically 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight or 80 parts by weight.
In the composite foaming material provided by the invention, the surface modified inorganic filler is a coupling agent modified inorganic filler, and is prepared by mixing the inorganic filler and the coupling agent; wherein the inorganic filler is preferably one or more of talcum powder, calcium carbonate, white carbon black, glass fiber, basalt fiber, montmorillonite and wollastonite, and more preferably calcium carbonate and/or glass fiber; the mass ratio of the calcium carbonate to the glass fiber is preferably 1 (0.5-2), and can be specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2; the particle size of the calcium carbonate is preferably 100-300 nm, and can be specifically 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm or 300nm; the diameter of the glass fiber is preferably 7 to 20. Mu.m, and may be specifically 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm; the length of the glass fiber is preferably 1-10 mm, and can be specifically 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm, 8.5mm, 9mm, 9.5mm or 10mm; the coupling agent is preferably one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent, and more preferably is maleic anhydride or an aluminum-titanium composite coupling agent; the mass ratio of the inorganic filler to the coupling agent is preferably 100 (1-10), and can be specifically 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9 and 100:10. In one embodiment provided by the invention, the surface modified inorganic filler is aluminum-titanium composite coupling agent modified calcium carbonate and/or silane coupling agent modified glass fiber; the mass ratio of the calcium carbonate to the aluminum-titanium composite coupling agent in the aluminum-titanium composite coupling agent modified calcium carbonate is preferably 100 (1-10), more preferably 100 (3-7), and particularly can be 100:5; the mass ratio of the glass fiber to the silane coupling agent in the silane coupling agent modified glass fiber is preferably 100 (1-10), more preferably 100 (1-5), and particularly can be 100:2.
In the composite foam material provided by the invention, the surface modified inorganic filler is preferably prepared according to the following steps: mixing inorganic filler with a coupling agent to obtain surface modified inorganic filler; wherein the temperature of the mixing is preferably 70-90 ℃, and can be specifically 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃; the mixing time is preferably 5-100 min, and specifically may be 5min, 10min, 15min, 20min, 25min, 30min, 40min, 50min, 60min, 70min, 80min, 90min or 100min.
In the composite foam material provided by the invention, the content of the surface-modified inorganic filler in the raw material may specifically be 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight, 14.5 parts by weight, 15 parts by weight, 15.5 parts by weight, 16 parts by weight, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight or 20 parts by weight.
In the composite foaming material provided by the invention, the cross-linking agent is one or more of dicumyl peroxide, dibenzoyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and peroxy hexane, preferably di-tert-butyl peroxide, and more preferably 1, 4-di-tert-butyl diisopropylbenzene peroxide. In one embodiment provided by the invention, the crosslinking agent is dicumyl peroxide and 1, 4-bis-tert-butyl dicumyl peroxide, and the mass ratio of dicumyl peroxide to 1, 4-bis-tert-butyl dicumyl peroxide is preferably 1 (0.5-2), and can be specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.
In the composite foaming material provided by the invention, the content of the cross-linking agent in the raw material substance can be specifically 0.1 part by weight, 0.11 part by weight, 0.12 part by weight, 0.13 part by weight, 0.14 part by weight, 0.15 part by weight, 0.16 part by weight, 0.17 part by weight, 0.18 part by weight, 0.19 part by weight, 0.2 part by weight, 0.21 part by weight, 0.22 part by weight, 0.23 part by weight, 0.24 part by weight, 0.25 part by weight, 0.26 part by weight, 0.27 part by weight, 0.28 part by weight, 0.29 part by weight or 0.3 part by weight.
In the composite foaming material provided by the invention, the raw material preferably further comprises a crosslinking auxiliary agent, and the crosslinking auxiliary agent is preferably triallyl isocyanurate; the content of the crosslinking agent in the raw material is preferably 0.05 to 0.5 part by weight, and specifically may be 0.05 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, or 0.5 part by weight.
In the composite foaming material provided by the invention, the compatibilizer is preferably styrene-acrylic acid-glycidyl methacrylate copolymer; the brand of the compatibilizer is ADR-E4370B, and the compatibilizer of the brand is provided by all chemical industry research companies of Shanxi province.
In the composite foaming material provided by the invention, the content of the compatibilizer in the raw material can be specifically 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight or 2.5 parts by weight.
In the composite foaming material provided by the invention, the plasticizer is preferably epoxidized soybean oil and/or citrate, and more preferably epoxidized soybean oil.
In the composite foam material provided by the invention, the content of the plasticizer in the raw material substance can be specifically 5 parts by weight, 5.2 parts by weight, 5.5 parts by weight, 5.7 parts by weight, 6 parts by weight, 6.2 parts by weight, 6.5 parts by weight, 6.7 parts by weight, 7 parts by weight, 7.2 parts by weight, 7.5 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.5 parts by weight, 8.7 parts by weight, 9 parts by weight, 9.2 parts by weight, 9.5 parts by weight, 9.7 parts by weight or 10 parts by weight.
In the composite foam material provided by the invention, the lubricant is preferably pentaerythritol stearate and/or ethylene distearate amide, and more preferably ethylene distearate amide.
In the composite foam material provided by the invention, the content of the lubricant in the raw material substance can be specifically 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 part by weight, 1.3 part by weight, 1.4 part by weight, 1.5 part by weight, 1.6 part by weight, 1.7 part by weight, 1.8 part by weight, 1.9 part by weight or 2 parts by weight.
In the composite foaming material provided by the invention, the antioxidant is antioxidant 1076 and/or antioxidant 168.
In the composite foaming material provided by the invention, the content of the antioxidant in the raw material can be specifically 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.55 part by weight, 0.6 part by weight, 0.65 part by weight, 0.7 part by weight, 0.75 part by weight, 0.8 part by weight, 0.85 part by weight, 0.9 part by weight, 0.95 part by weight or 1 part by weight.
The invention also provides a preparation method of the degradable biomass composite foaming material, which comprises the following steps:
a) Melt blending polylactic acid, a flexible polymer, surface modified straw fiber, surface modified inorganic filler, a cross-linking agent, a compatibilizer, a plasticizer, a lubricant and an antioxidant to obtain a material to be foamed;
b) And foaming the material to be foamed to obtain the degradable biomass composite foaming material.
In the preparation method provided by the invention, in the step a), the polylactic acid, the flexible polymer, the surface modified straw fiber, the surface modified inorganic filler, the cross-linking agent, the compatibilizer, the plasticizer, the lubricant and the antioxidant are preferably premixed before being subjected to melt blending; the temperature of the premixing is preferably 15 to 35 ℃, and may be specifically 25 ℃ (room temperature).
In the preparation method provided by the present invention, in the step a), the temperature of the melt blending is preferably 100 to 190 ℃, specifically, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, or 190 ℃.
In one embodiment provided by the present invention, in step a), the melt blending is performed in a twin screw extruder; the screw rotating speed of the double-screw extruder is preferably 60-120 r/min, and can be specifically 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min or 120r/min; the temperature of the first area of the double-screw extruder is preferably 100-150 ℃, the temperature of the second area is preferably 165-180 ℃, the temperature of the third area is preferably 185-190 ℃, the temperature of the fourth area is preferably 180-190 ℃, the temperature of the fifth area is preferably 165-170 ℃, and the temperature of the machine head is preferably 150-175 ℃.
In the preparation method provided by the invention, in the step b), the foaming mode is preferably physical foaming, and the foaming agent is preferably high-pressure CO 2 Fluid or high pressure N 2 A fluid; the equipment used for foaming is preferably a supercritical mould pressing foaming machine; the foaming temperature is preferably 60-180deg.C, and can be specifically 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C or more180 ℃; the pressure of the foaming is preferably 5-20 MPa, and can be specifically 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa, 18MPa, 19MPa or 20MPa; the pressurizing time of the foaming is preferably 1-5 h, and can be specifically 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h; the pressure release time of the foaming is preferably 0.1 to 20s, and may be specifically 0.1s, 0.5s, 1s, 2s, 3s, 4s, 5s, 7s, 10s, 12s, 15s, 17s or 20s.
The invention also provides a degradable biomass composite foaming sheet material, which is prepared from the technical scheme.
According to the invention, the component composition of the foaming material is optimally designed, so that the production cost of the foaming material is obviously reduced, and the comprehensive performance of the foaming material is improved; specifically, the key points of the technical scheme of the invention are as follows: 1) The biodegradable rigid polymer PLA and the flexible polymer are subjected to a physical blending modification method to form a composite material, and cheap straw fibers and inorganic fillers are added into the system, so that the cost of the foaming material is reduced, and meanwhile, the foaming material has good biodegradability, can be completely biodegraded, and is environment-friendly; 2) The compatibility between matrix polymers in the composite material is promoted by utilizing the synergism of the compatibilizer and the cross-linking agent, the chemical reaction between molecular chain segments of the rigid polymer and the flexible polymer and the melt strength of the composite material are enhanced, so that the foaming performance and the mechanical performance of the composite foaming material are further improved; 3) By carrying out surface modification on the straw fibers and the inorganic filler, the interfacial binding force between the straw fibers and the inorganic filler and the polymer matrix is enhanced, the dispersibility of the straw fibers and the inorganic filler in the matrix is improved, and the mechanical property of the foaming material can be obviously improved.
The technical scheme provided by the invention at least comprises the following advantages: 1) The composite foaming material provided by the invention has good mechanical property, low price, complete biodegradation and reasonable utilization of waste biomass straw fibers, and has great practical significance and profound historical significance in protecting environment and saving resources; 2) Compared with the prior art, the preparation method of the composite foaming material is simple, high in production efficiency, large in scale production, large in multiplying power adjustable range and good in heat preservation performance, the foaming mode preferably adopts physical foaming, and has the advantages of environment friendliness, safety and the like, substances such as formamide or a foaming agent cannot be remained in a finished product, and the substances cannot have certain influence on a human body, so that a foundation is provided for the research and application fields of the biodegradable polyester/straw fiber full-biodegradable composite material, and the prepared foaming material can be used for a disposable fresh-keeping and refrigerating container and the like; 3) In the preparation process of the composite foaming material, chemical crosslinking and physical crosslinking are formed between polymer matrixes, so that the improvement of compatibility improves the interfacial binding force of the polymer matrixes, and the foaming material with excellent performance obtained by adjustment has great advantages; 4) According to the invention, the surface modification is carried out on the inorganic filler, so that the interfacial binding force and dispersibility between the polymer matrix and the inorganic filler are obviously improved, the problem of dispersibility between the matrix and the inorganic filler is solved, and the foaming material with excellent performance can be obtained; 5) According to the invention, the surface of the straw fiber is modified, so that better interface bonding is formed between the polymer matrix and the straw fiber, the interface acting force is enhanced, and the comprehensive performance of the composite material is improved.
For the sake of clarity, the following examples and comparative examples are described in detail.
In the following examples and comparative examples of the present invention, the surface-modified straw fiber used was prepared as follows:
putting soybean (or straw) stalk into a pulverizer to pulverize to obtain short soybean (or straw) stalk fiber, screening raw materials with granularity less than 800 μm by adopting a mesh sieve, discarding oversize materials, collecting undersize stalk powder, and drying for 12h at 70 ℃ to reduce the water content to below 1%; 100 parts by weight of the straw powder was then mixed with 5 parts by weight of maleic anhydride in a high speed mixer at 90 ℃ for 30 minutes to obtain a surface modified soybean (or straw) straw fiber.
In the following examples and comparative examples of the present invention, the surface-modified calcium carbonate used was prepared as follows:
100 parts by weight of calcium carbonate with the particle size of 220nm and 5 parts by weight of an aluminum-titanium composite coupling agent (model number OL-AT1618, all of Shanxi chemical research Co., ltd.) are placed in a high-speed stirrer and stirred AT 80 ℃ for 15 minutes, so as to obtain the surface-modified calcium carbonate.
In the following examples and comparative examples of the present invention, the surface-modified glass fiber used was prepared as follows:
100 parts by weight of glass fiber (chopped glass fiber, diameter 13 μm, length 3.0 to 4.5mm, model TCR438G, mount Taishan glass fiber Co., ltd.) and 2 parts by weight of silane coupling agent (Nanjing product Ning coupling agent Co., model A-172) were placed in a high-speed mixer and stirred at 90℃for 90 minutes to obtain surface-modified glass fiber.
Example 1
80 parts by weight of PLA with a weight average molecular weight of 15 ten thousand, 20 parts by weight of PBST with a weight average molecular weight of 25 ten thousand (the molar ratio of the polybutylene succinate chain segment to the polybutylene terephthalate chain segment is about 60/40), 80 parts by weight of surface-modified soybean straw fiber, 10 parts by weight of surface-modified calcium carbonate, 10 parts by weight of surface-modified glass fiber, 0.3 part by weight of cross-linking agent 1, 4-di-tert-butyl diisopropylbenzene peroxide, 2.5 parts by weight of compatibilizer (styrene-acrylic acid-glycidyl methacrylate copolymer polymer, brand: ADR-E4370B, the same applies hereinafter), 10 parts by weight of plasticizer (epoxidized soybean oil, the same applies hereinafter), 2 parts by weight of lubricant (ethylene bis stearamide, the same applies hereinafter) and 1 part by weight of antioxidant (antioxidant 1076, the same applies hereinafter) are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, and the temperatures of a charging barrel and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first region, 165-180 ℃ in a second region, 185-190 ℃ in a third region, 180-190 ℃ in a fourth region, 165-170 ℃ in a fifth region and 150-175 ℃ in the machine head, so as to obtain the composite modified granule.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is quickly released for 2s,and after the pressure in the die cavity is released completely, opening the die to obtain the degradable biomass composite foaming sheet material.
Example 2
70 parts by weight of PLA with a weight average molecular weight of 20 ten thousand, 30 parts by weight of PBST with a weight average molecular weight of 28 ten thousand (the molar ratio of the polybutylene succinate segment to the polybutylene terephthalate segment is about 50/50), 70 parts by weight of surface-modified soybean straw fiber, 5 parts by weight of surface-modified calcium carbonate, 10 parts by weight of surface-modified glass fiber, 0.2 part by weight of cross-linking agent 1, 4-di-tert-butyl diisopropylbenzene peroxide, 2.0 parts by weight of compatibilizer, 8 parts by weight of plasticizer, 0.8 parts by weight of lubricant and 0.8 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Example 3
60 parts by weight of PLA with a weight average molecular weight of 28 ten thousand, 40 parts by weight of PBST with a weight average molecular weight of 30 ten thousand (the molar ratio of the polybutylene succinate segment to the polybutylene terephthalate segment is about 40/60), 60 parts by weight of surface-modified soybean straw fiber, 5 parts by weight of surface-modified calcium carbonate, 5 parts by weight of surface-modified glass fiber, 0.3 part by weight of cross-linking agent 1, 4-di-tert-butyl diisopropylbenzene peroxide, 2.5 parts by weight of compatibilizer, 8 parts by weight of plasticizer, 0.8 part by weight of lubricant and 0.8 part by weight of antioxidant are placed in a high-speed mixer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Example 4
50 parts by weight of PLA with a weight average molecular weight of 32 ten thousand, 50 parts by weight of PBST with a weight average molecular weight of 33 ten thousand (the molar ratio of the butylene succinate chain segment to the butylene terephthalate chain segment is about 50/50), 50 parts by weight of surface modified soybean straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of surface modified glass fiber, 0.1 part by weight of cross-linking agent 1, 4-di-tert-butyl diisopropyl peroxide, 2.5 parts by weight of compatibilizer, 5 parts by weight of plasticizer, 0.5 part by weight of lubricant and 0.5 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Example 5
70 parts by weight of PLA with a weight average molecular weight of 35 ten thousand, 30 parts by weight of PBST with a weight average molecular weight of 38 ten thousand (the molar ratio of the butylene succinate chain segment to the butylene terephthalate chain segment is about 50/50), 50 parts by weight of surface modified soybean straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of surface modified glass fiber, 0.2 part by weight of cross-linking agent 1, 4-di-tert-butyl diisopropyl peroxide, 1.5 parts by weight of compatibilizer, 5 parts by weight of plasticizer, 1 part by weight of lubricant and 1 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Example 6
A degradable biomass composite foamed sheet was prepared by the method of reference example 1, except that "10 parts by weight of surface-modified calcium carbonate and 10 parts by weight of glass fiber" was replaced with 20 parts by weight of surface-modified calcium carbonate.
Example 7
A degradable biomass composite foamed sheet was prepared by the method of reference example 1, except that "10 parts by weight of surface-modified calcium carbonate and 10 parts by weight of glass fiber" was replaced with 20 parts by weight of glass fiber.
Example 8
50 parts by weight of PLA with a weight average molecular weight of 35 ten thousand, 20 parts by weight of PBST with a weight average molecular weight of 45 ten thousand (the molar ratio of the butylene succinate chain segment to the butylene terephthalate chain segment is about 60/40), 15 parts by weight of PCL with a weight average molecular weight of 29 ten thousand, 15 parts by weight of PBS with a weight average molecular weight of 21 ten thousand, 50 parts by weight of surface modified soybean straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of surface modified glass fiber, 0.2 part by weight of cross-linking agent 1, 4-bis-tert-butyl-diisopropylbenzene peroxide, 1.5 parts by weight of compatibilizer, 8 parts by weight of plasticizer, 0.5 part by weight of lubricant and 0.5 part by weight of antioxidant are placed in a high-speed mixer at room temperature and uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Example 9
50 parts by weight of PLA with a weight average molecular weight of 22 ten thousand, 50 parts by weight of PBST with a weight average molecular weight of 40 ten thousand (the molar ratio of the butylene succinate chain segment to the butylene terephthalate chain segment is about 50/50), 50 parts by weight of surface modified soybean straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of surface modified glass fiber, 0.15 part by weight of crosslinking agent dicumyl peroxide, 0.15 part by weight of crosslinking agent 1, 4-di-tert-butyl dicumyl peroxide, 0.2 part by weight of crosslinking auxiliary agent triallyl isocyanurate, 2 parts by weight of compatibilizer, 7 parts by weight of plasticizer, 1 part by weight of lubricant and 0.8 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is quickly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is openedAnd (5) molding to obtain the degradable biomass composite foaming sheet material.
Example 10
50 parts by weight of PLA with a weight average molecular weight of 29 ten thousand, 50 parts by weight of PBST with a weight average molecular weight of 40 ten thousand (the molar ratio of the butylene succinate chain segment to the butylene terephthalate chain segment is about 50/50), 30 parts by weight of surface-modified soybean straw fiber, 20 parts by weight of surface-modified rice straw fiber, 10 parts by weight of surface-modified calcium carbonate, 10 parts by weight of surface-modified glass fiber, 0.2 part by weight of cross-linking agent 1, 4-di-tert-butyl-diisopropylbenzene peroxide, 2 parts by weight of compatibilizer, 7 parts by weight of plasticizer, 1 part by weight of lubricant and 0.8 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 90r/min, the temperatures of a feed cylinder and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in a first area, 165-180 ℃ in a second area, 185-190 ℃ in a third area, 180-190 ℃ in a fourth area, 165-170 ℃ in a fifth area and 150-175 ℃ in the machine head, and the modified granules are compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 20MPa, the pressure is kept for 3 hours, the pressure is rapidly released for 2 seconds, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Comparative example 1
Uniformly mixing 70 parts by weight of PLA with a weight average molecular weight of 26 ten thousand, 30 parts by weight of PBST with a weight average molecular weight of 40 ten thousand, 50 parts by weight of non-surface-modified straw fiber, 10 parts by weight of non-surface-modified calcium carbonate, 10 parts by weight of glass fiber, 0.2 part by weight of cross-linking agent, 1.5 parts by weight of compatibilizer, 5 parts by weight of plasticizer, 1 part by weight of lubricant and 1 part by weight of antioxidant in a high-speed stirrer at room temperature; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 60-120r/min, the temperatures of a charging barrel and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in the first region, 165-180 ℃ in the second region, 185-190 ℃ in the third region, 180-190 ℃ in the fourth region, 165-170 ℃ in the fifth region and 150-175 ℃ in the machine head, and the modified granule is compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 60-180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 5-20 MPa, the pressure is kept for 1-5 h, the pressure is rapidly released for 0.1-20 s, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Comparative example 2
Uniformly mixing 70 parts by weight of PLA with a weight average molecular weight of 40 ten thousand, 30 parts by weight of PBST with a weight average molecular weight of 28 ten thousand, 50 parts by weight of surface modified straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of glass fiber, 5 parts by weight of plasticizer, 1 part by weight of lubricant and 1 part by weight of antioxidant in a high-speed stirrer at room temperature; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 60-120r/min, the temperatures of a charging barrel and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in the first region, 165-180 ℃ in the second region, 185-190 ℃ in the third region, 180-190 ℃ in the fourth region, 165-170 ℃ in the fifth region and 150-175 ℃ in the machine head, and the modified granule is compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 60-180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 5-20 MPa, the pressure is kept for 1-5 h, the pressure is rapidly released for 0.1-20 s, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Comparative example 3
100 parts by weight of PLA with a weight average molecular weight of 40 ten thousand, 50 parts by weight of surface modified straw fiber, 10 parts by weight of surface modified calcium carbonate, 10 parts by weight of glass fiber, 0.2 part by weight of cross-linking agent, 1.5 parts by weight of compatibilizer, 5 parts by weight of plasticizer, 1 part by weight of lubricant and 1 part by weight of antioxidant are placed in a high-speed stirrer at room temperature to be uniformly mixed; and then extruding and granulating by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 60-120r/min, the temperatures of a charging barrel and each section of a machine head of the double-screw extruder are respectively 100-150 ℃ in the first region, 165-180 ℃ in the second region, 185-190 ℃ in the third region, 180-190 ℃ in the fourth region, 165-170 ℃ in the fifth region and 150-175 ℃ in the machine head, and the modified granule is compounded.
Placing the obtained composite modified granules in a supercritical mould pressing foaming machine, heating the mould pressing foaming machine to 60-180 ℃ in advance, closing the mould, and introducing a physical foaming agent CO 2 The pressure is 5-20 MPa, the pressure is kept for 1-5 h, the pressure is rapidly released for 0.1-20 s, and after the pressure in the die cavity is completely released, the die is opened, so that the degradable biomass composite foaming sheet material is obtained.
Performance testing
The mechanical property testing method comprises the following steps: the national standard GB/T8804.2-2003 "measurement of tensile Property of thermoplastic sheet".
The density and foaming ratio testing method comprises the following steps: the apparent density of the foamed material was obtained by a drainage method using an electron densitometer according to the GB/T6343-2009 standard test. The foaming ratio of the obtained foaming material is calculated by a formula: b=ρ 1 /ρ 2 Wherein b is the expansion ratio, ρ 1 Density, ρ, of the base resin of the blend 2 Is the apparent density of the foaming material.
Biodegradation performance test: the biological degradation performance of the blend foaming material is tested by adopting a composting method, and the composting degradation test is carried out according to the GB/T19277.1-2011 method, wherein the composting time is 20 days.
The foamed sheets prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to performance test, and the results are shown in Table 1:
table 1 results of performance test of foamed sheet
| Performance index | Expansion ratio | Density of | Tensile Strength | Elongation at break | Compressive Strength | Biological decomposition Rate |
| Example 1 | 4.1 times | 0.42kg/m 3 | 8.9MPa | 38％ | 4.6MPa | 55％ |
| Example 2 | 5.5 times | 0.46kg/m 3 | 8.1MPa | 47％ | 4.4MPa | 49％ |
| Example 3 | 6.8 times | 0.51kg/m 3 | 7.3MPa | 54％ | 4.1MPa | 46％ |
| Example 4 | 7.9 times | 0.52kg/m 3 | 6.2MPa | 63％ | 3.9MPa | 40％ |
| Example 5 | 7.3 times | 0.48kg/m 3 | 8.4MPa | 40％ | 4.3MPa | 43％ |
| Example 6 | 4.8 times | 0.39kg/m 3 | 6.4MPa | 30％ | 4.9MPa | 62％ |
| Example 7 | 3.6 times | 0.62kg/m 3 | 9.1MPa | 43％ | 3.3MPa | 40％ |
| Example 8 | 8.8 times | 0.48kg/m 3 | 5.7MPa | 50％ | 3.1MPa | 45％ |
| Example 9 | 6.7 times | 0.58kg/m 3 | 7.9MPa | 81％ | 4.7MPa | 34％ |
| Example 10 | 8.3 times | 0.50kg/m 3 | 6.9MPa | 67％ | 4.5MPa | 50％ |
| Comparative example 1 | 5.7 times | 0.53kg/m 3 | 5.2MPa | 27％ | 4.0MPa | 47％ |
| Comparative example 2 | 4.4 times | 0.49kg/m 3 | 4.8MPa | 32％ | 4.1MPa | 48％ |
| Comparative example 3 | 7.1 time of | 0.51kg/m 3 | 10.6MPa | 10％ | 6.2MPa | 43％ |
As can be seen from Table 1, comparative example 3 was poor in mechanical properties without the addition of the flexible polymer, and examples 1 to 4, in which 20 parts, 30 parts, 40 parts and 50 parts of PBST were added, respectively, and the elongation at break was increased in order, respectively, to 38%, 47%, 54% and 63%, but the tensile strengths were slightly decreased, respectively, to 8.9MPa, 8.1MPa, 7.3MPa and 6.2MPa, and in addition, the compressive strengths were slightly decreased with the increase of the flexible polymer, indicating that the addition of the flexible polymer can regulate the mechanical properties of the foaming material.
It can be seen from examples 1 to 4 that the increase of the straw fiber content can increase the biodegradation rate of the foamed sheet, which is beneficial to the biodegradability of the foamed sheet.
It can be seen from example 5 and comparative example 1 that the surface-modified fiber can effectively improve the foaming ratio and mechanical properties of the foamed sheet.
As can be seen from example 5 and comparative example 2, the tensile strength of the foamed sheet without the compatibilizer and the crosslinking agent is only 4/7 of that of example 5, and in example 5, one end of the compatibilizer is connected with a section of rigid polymer chain in the preparation process, and the rigid polymer phase and the flexible polymer phase are tightly connected together through entanglement of the molecular chains, so that the interfacial bonding force of the two phases is remarkably improved, and the crosslinking agent enables the rigid polymer and the flexible polymer to undergo self-crosslinking reaction, so that the melt strength is improved, and the foaming property and the mechanical property are remarkably improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The degradable biomass composite foaming material is prepared by foaming after melt blending of raw materials, and the raw materials comprise, by weight:
the flexible polymer is one or more of poly (butylene succinate/terephthalate), poly (butylene succinate-terephthalate), poly (butylene succinate/adipate) and polycaprolactone;
the surface modified straw fiber is a coupling agent modified straw fiber, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent;
the surface modified inorganic filler is a coupling agent modified inorganic filler, and the coupling agent is one or more of maleic anhydride, a silane coupling agent and an aluminum-titanium composite coupling agent;
the cross-linking agent is one or more of dicumyl peroxide, dibenzoyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide and peroxy hexane;
the compatibilizer is styrene-acrylic acid-glycidyl methacrylate copolymer.
2. The degradable biomass composite foam material according to claim 1, wherein the total weight part of the polylactic acid and the flexible polymer in the raw material is 100 parts.
3. The degradable biomass composite foam material according to claim 1, wherein the straw fiber in the coupling agent modified straw fiber is one or more of straw fiber, wheat straw fiber, sugarcane straw fiber, soybean straw fiber and corn straw fiber.
4. The degradable biomass composite foaming material according to claim 1, wherein the inorganic filler in the coupling agent modified inorganic filler is one or more of talcum powder, calcium carbonate, white carbon black, glass fiber, basalt fiber, montmorillonite and wollastonite.
5. The degradable biomass composite foam material according to claim 1, wherein the plasticizer is epoxidized soybean oil and/or citrate.
6. The degradable biomass composite foam material according to claim 1, wherein the lubricant is pentaerythritol stearate and/or ethylene bis-stearamide.
7. The degradable biomass composite foaming material according to claim 1, wherein the antioxidant is antioxidant 1076 and/or antioxidant 168.
8. A method for preparing the degradable biomass composite foaming material according to any one of claims 1 to 7, comprising the following steps:
a) Melt blending polylactic acid, a flexible polymer, surface modified straw fiber, surface modified inorganic filler, a cross-linking agent, a compatibilizer, a plasticizer, a lubricant and an antioxidant to obtain a material to be foamed;
b) And foaming the material to be foamed to obtain the degradable biomass composite foaming material.
9. The method according to claim 8, wherein in step b), the foaming is performed by physical foaming; the foaming temperature is 60-180 ℃; the foaming pressure is 5-20 MPa; the foaming pressurization time is 1-5 h; the pressure release time of the foaming is 0.1-20 s.
10. The degradable biomass composite foaming sheet material is characterized in that the material is any one of the degradable biomass composite foaming materials of 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310696259.3A CN116535838A (en) | 2023-06-13 | 2023-06-13 | Degradable biomass composite foaming material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310696259.3A CN116535838A (en) | 2023-06-13 | 2023-06-13 | Degradable biomass composite foaming material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116535838A true CN116535838A (en) | 2023-08-04 |
Family
ID=87445433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310696259.3A Pending CN116535838A (en) | 2023-06-13 | 2023-06-13 | Degradable biomass composite foaming material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535838A (en) |
-
2023
- 2023-06-13 CN CN202310696259.3A patent/CN116535838A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525487B (en) | Composite material degraded by environment and preparation method thereof | |
| CN107629426B (en) | Bamboo fiber/polylactic acid composite material and preparation method thereof | |
| CN109401243B (en) | High-toughness bio-based polylactic acid/reactive modified rubber thermoplastic vulcanized rubber blending material and secondary reaction extrusion preparation method thereof | |
| CN105504363A (en) | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method | |
| CN101481507B (en) | Wholly-degradable material, preparation thereof and method for preparing packing bag with the same | |
| CN101591467A (en) | A kind of polylactic wood/plastic composite material and preparation method thereof | |
| CN103849018A (en) | Rice hull ash/macromolecular composite material, preparation method and application thereof | |
| CN103642184A (en) | Dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof | |
| CN111410822B (en) | PBAT/PLA starch-based completely biodegradable material and preparation method thereof | |
| CN113583405A (en) | High-performance fully-degradable composite material and preparation method thereof | |
| CN113234327A (en) | Method for producing degradable plastic from bagasse | |
| CN111518334A (en) | Method for recycling and preparing modified polypropylene composite material from waste polypropylene pipeline | |
| CN113354934A (en) | Full-biodegradable blending material | |
| CN113549280A (en) | Preparation method of aging-resistant ethylene propylene rubber powder-based EVA (ethylene-vinyl acetate) thermoplastic elastomer sealing element | |
| CN101153119A (en) | Clubbed composite material of wood-wool and plastics, and method of producing the same | |
| CN116535838A (en) | Degradable biomass composite foaming material and preparation method and application thereof | |
| CN113512275A (en) | High-melt-strength compostable degradable material and preparation method thereof | |
| CN115521535B (en) | High-impact recycled polypropylene resin material and preparation method thereof | |
| CN115490950B (en) | Solvent-resistant modified polyethylene and preparation method thereof | |
| CN111073229A (en) | Biodegradable master batch containing modified papermaking waste and preparation method thereof | |
| CN113788980B (en) | Pre-swelling continuous extrusion foaming polylactic acid material and preparation method and application thereof | |
| KR101208107B1 (en) | Manufacturing method of plastic for car interior material using biomass pellet and thereof | |
| CN113637302A (en) | Modified biodegradable polylactic acid foaming particle and preparation process thereof | |
| CN113045867A (en) | Preparation method of degradable composite material based on modified hemp fibers | |
| Akdoğan et al. | Natural fiber thermoplastic composites in terms of new production technologies: A review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |