CN115093667A - Durable PLA/plant fiber low-carbon composite material and preparation method thereof - Google Patents
Durable PLA/plant fiber low-carbon composite material and preparation method thereof Download PDFInfo
- Publication number
- CN115093667A CN115093667A CN202210546273.0A CN202210546273A CN115093667A CN 115093667 A CN115093667 A CN 115093667A CN 202210546273 A CN202210546273 A CN 202210546273A CN 115093667 A CN115093667 A CN 115093667A
- Authority
- CN
- China
- Prior art keywords
- modified
- parts
- pla
- durable
- plant 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
- 239000000835 fiber Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000011347 resin Substances 0.000 claims abstract description 72
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 239000000806 elastomer Substances 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 241001474374 Blennius Species 0.000 claims abstract description 8
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims abstract description 4
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims abstract description 4
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims abstract description 4
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims abstract 7
- 241000196324 Embryophyta Species 0.000 claims description 79
- 238000002156 mixing Methods 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 45
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052621 halloysite Inorganic materials 0.000 claims description 19
- 235000021355 Stearic acid Nutrition 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000008117 stearic acid Substances 0.000 claims description 18
- 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 17
- 238000001125 extrusion Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- 229920001661 Chitosan Polymers 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 15
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 14
- 239000010902 straw Substances 0.000 claims description 14
- 238000004381 surface treatment Methods 0.000 claims description 14
- 240000007594 Oryza sativa Species 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 235000007164 Oryza sativa Nutrition 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 235000009566 rice Nutrition 0.000 claims description 11
- 102000002067 Protein Subunits Human genes 0.000 claims description 10
- 108010001267 Protein Subunits Proteins 0.000 claims description 10
- 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 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 9
- 230000002687 intercalation Effects 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 7
- 239000004593 Epoxy Chemical group 0.000 claims description 7
- 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 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 229960003638 dopamine Drugs 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 241001468265 Candidatus Phytoplasma Species 0.000 claims description 6
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- -1 poly propylene carbonate Polymers 0.000 claims description 4
- 229910052613 tourmaline Inorganic materials 0.000 claims description 4
- 229940070527 tourmaline Drugs 0.000 claims description 4
- 239000011032 tourmaline Substances 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 240000000797 Hibiscus cannabinus Species 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 3
- 239000005871 repellent Substances 0.000 claims description 3
- 239000013053 water resistant agent Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000002071 nanotube Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 229920002988 biodegradable polymer Polymers 0.000 description 3
- 239000004621 biodegradable polymer Substances 0.000 description 3
- 239000011174 green composite Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, relating to the technical field of polymer composite materials; the composite material comprises the following components: 20-90 parts of modified biodegradable matrix resin; 0-50 parts of modified plant fiber; 1-5 parts of modified composite diatomite; 5-10 parts of high-impact PA11/PETG elastomer; 0-6 parts of modified seaweed powder; 1-5 parts of a crosslinking agent; 1-5 parts of a comprehensive auxiliary agent; the modified biodegradable matrix resin comprises a first modified resin and a second modified resin; the first modified resin is PPC, and the second modified resin comprises one or more modified resins of PBAT, PCL, PLA, PBS, PBSA, PBST, PHB, PHA, PVA and PHBV; the production and preparation of the biodegradable low-carbon composite material with high strength and durability are realized.
Description
Technical Field
The application relates to the technical field of polymer composite materials, in particular to a durable PLA/plant fiber low-carbon composite material and a preparation method thereof.
Background
From a material perspective, we on the one hand strongly motivated the use of biodegradable plastics to replace traditional petroleum-based plastics; on the other hand, agricultural and forestry wastes and negative carbon materials are required to be used well. If we define the petroleum-based plastic as "positive carbon material (manufactured and discharged carbon dioxide)"; materials that consume or absorb carbon dioxide during the manufacturing process are referred to as "negative carbon materials"; the material which does not discharge carbon dioxide and does not absorb carbon dioxide in the manufacturing process is called 'zero carbon material'; while the carbon footprint of plant-based or biodegradable plastics is typically only 50-70% of that of petroleum-based plastics, it can be referred to as "green material"; then the material having a carbon footprint intermediate between that of the plant-based biodegradable material and the "zero carbon material" may be referred to as a "low carbon material".
On the other hand, widespread petroleum-based plastics have spread throughout various industries and even have reached a flood. In particular, online shopping and take-away are started, so that the non-degradable traditional petroleum-based plastics form 'white pollution' which destroys the ecological environment and further causes threats and hazards to various organisms and even human beings through the food chain. Therefore, the popularization of the green biodegradable polymer becomes the best scheme for solving the plastic waste.
However, although the corresponding biodegradable materials exist in the industry, more problems still exist, and the materials have larger application limitations; if the product is easily decomposed by oxidation, light degradation, microorganism and water vapor, the service life is short; the application range is limited due to poor thermal stability and physical strength of the product, so that the problem in the industry needs to be overcome to provide a durable low-carbon composite material.
Disclosure of Invention
The application aims to provide a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, so as to realize the preparation of the low-carbon composite material which has high strength and durability and can be biodegraded.
In order to achieve the technical purpose, the application provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, and in a first aspect, the application provides a durable PLA/plant fiber low-carbon composite material: the composite material comprises the following components:
20-90 parts of modified biodegradable matrix resin;
0-50 parts of modified plant fiber;
1-5 parts of modified composite diatomite;
5-10 parts of high-impact PA11/PETG elastomer;
0-6 parts of modified seaweed powder;
1-5 parts of a crosslinking agent;
1-5 parts of a comprehensive auxiliary agent;
the modified biodegradable matrix resin comprises a first modified resin and a second modified resin;
the first modified resin is PPC (poly propylene carbonate), and the second modified resin comprises one or more modified resins of PBAT, PCL, PLA, PBS, PBSA, PBST, PHB, PHA, PVA and PHBV.
Preferably, the modified biodegradable matrix resin consists of modified PPC, modified PLA and modified PBS.
Preferably, the proportion of the modified PPC, the modified PLA and the modified PBS in the composite material is
10-15 parts of modified PPC;
5-54 parts of modified PLA;
0-30 parts of modified PBS.
Preferably, the modification process of the modified biodegradable matrix resin comprises the following steps:
solid-phase grafting reaction: respectively placing the modified biodegradable matrix resin in a vacuum drier for drying for 50-70 minutes, then adding the composite tourmaline additive and the grafting agent, carrying out ultraviolet irradiation, and adding into a high-speed mixer for mixing to obtain the biodegradable matrix resin after solid phase grafting;
melt grafting reaction: respectively putting the solid-phase grafted biodegradable matrix resin into different high-speed mixers, and putting maleic anhydride and DCP for fully mixing.
Preferably, in the step of solid phase grafting reaction, the rotation speed of the high-speed mixer is 1000-1300 rpm, and the mixing time is 25-35 minutes.
Preferably, the modification process of the modified plant fiber or the modified seaweed powder comprises the following steps:
a1, putting the plant protomer into a vacuum rotary heating drier, and stirring and drying for 1-2 hours at 80-100 ℃;
a2, introducing oxygen gas flow, opening an ion source in a vacuum drier, and carrying out plasma treatment for 3-6 minutes while stirring;
a3, surface treatment of the first layer: spraying stearic acid and acetic anhydride under ultraviolet irradiation, and then irradiating for 5-10 minutes while stirring;
a4, surface treatment of the second layer: spraying stearic acid coupling agent, and stirring for 3-5 minutes under the irradiation of an ultraviolet lamp;
a5, surface treatment of the third layer: spraying PVA water solution and cross-linking agent, and stirring for 3-5 min under the irradiation of ultraviolet lamp.
Preferably, the plant protomer comprises one or more of bamboo fiber, straw fiber of MAI, sisal fiber, kenaf fiber, rice straw fiber, rice hull powder or microalgae powder;
when the plant protomer is more than one, the modification process of different plant protomers is independently carried out.
Preferably, in step a3, the stearic acid coupling agent is 1% by mass of the phytoplasma; acetic anhydride represents 1% of the mass of the phytoplasma.
Preferably, the modification process of the modified composite diatomite comprises the following steps:
b1, adding halloysite, a silane coupling agent, epoxidized soybean oil and stearic acid into a high-speed mixer, and stirring at a high speed, mixing and activating;
b2, further adding an antioxidant 1010, an antioxidant 168 and chitosan into the mixture obtained in step B2, and stirring and mixing to obtain casing polysaccharide intercalation halloysite;
b3, feeding the perianoglycan intercalation halloysite into a kneader, adding dopamine, PVA resin and kieselguhr, and mixing for 5-10 minutes at 90-130 ℃;
and B4, putting the mixture obtained in the step B3 into a double-screw granulator, and extruding and granulating at the temperature of 120-160 ℃.
Preferably, in step B1, the mass parts of the components are respectively: 100 parts of halloysite, 1 part of silane coupling agent, 1 part of epoxidized soybean oil and 1 part of stearic acid;
in step B2, the components are, in parts by mass:
1010 parts of antioxidant, 10 parts; antioxidant 168, 10 parts; 30 parts of chitosan;
in step B3, the components are, in parts by mass: 1 part of dopamine, 5 parts of PVA resin and 300 parts of diatomite.
Preferably, the preparation of the high impact PA11/PETG elastomer comprises the following steps:
c1, mixing PA11, glycerol, formamide and benzene sulfonamide plasticizer in a high-speed mixer for 30-60 minutes at a high speed, and standing for later use;
c2, placing PETG, epoxy chain extender (ADR 4468), PPC and polyethylene glycol in another high-speed mixer, and mixing for 30-50 minutes at high speed;
c3, mixing the mixture obtained after the standing in the step C1 with the mixture obtained in the step C2, adding DCP (dicumyl peroxide) and GMA (glycidyl methacrylate), and mixing for 10-15 minutes;
c4, putting the mixture uniformly mixed in the step C3 into a double-screw extruder for compatibilization grafting reaction; the extrusion granulation temperature is 160-190 ℃, and the high impact PA11/PETG elastomer is obtained.
Preferably, in step C1, the ratio of each component is: PA11, 85%; 3% of glycerol; formamide, 2%; benzenesulfonamide plasticizer, 7%; standing for 6 hours;
in step C2, the ratio of each component is: PETG, 90%; epoxy chain extender (ADR 4468), 1%; PPC, 5%; 4% of polyethylene glycol;
in the step C3, the ratio of the mixture in the step C1 to the mixture in the step C2 is 3:7, and the DCP and the GMA respectively account for 0.1% and 3% of the mass of the mixture mixed in the step C3.
Preferably, the crosslinking agent consists of superfine barium sulfate, water-resistant agent carbodiimide and MDI (diphenyl methane diisocyanate).
Preferably, the ratio of each component of the cross-linking agent is as follows: ultra-fine barium sulfate: water repellent carbodiimide: MDI =2:2: 1.
Preferably, the comprehensive aid consists of calcium stearate, PE wax and an antioxidant 1010.
Preferably, the comprehensive auxiliary agent comprises the following components in proportion: calcium stearate: PE wax: antioxidant 1010=4-6:2-4: 1-3.
Preferably, the composition of the composite material is:
37 parts of modified biodegradable matrix resin;
46 parts of modified plant fiber;
4 parts of modified composite diatomite;
high impact PA11/PETG elastomer, 8 parts;
3 parts of a crosslinking agent;
and 2 parts of a comprehensive assistant.
In a second aspect, the present application provides a method for preparing a durable PLA/plant fiber low carbon composite material, for preparing any of the above composite materials, comprising the steps of:
putting the components in parts by proportion into a high mixing machine for mixing, feeding the uniformly mixed mixture into a double-screw extruder for micro-crosslinking reaction granulation, wherein the extrusion temperature is 160-190 ℃, and obtaining the durable PLA/plant fiber low-carbon composite material.
Compared with the prior art, the beneficial effect of this application lies in:
(1) the modified biodegradable matrix resin is modified by adopting a two-stage composite grafting technology, so that the compatibility and the binding force between biodegradable macromolecules or between the biodegradable macromolecules and other macromolecules (bio-based non-degradable materials or petroleum-based resin) are improved;
(2) the plant fiber is adopted as the raw material, and the agricultural waste is changed into valuable; the compatibility problem when the plant fiber is utilized in the industry is overcome by modifying the plant fiber and carrying out three-layer surface treatment;
(3) two kinds of blocking and anti-degradation slow-release materials are adopted, and a long-acting and short-acting blocking and anti-degradation method is utilized, so that the degradation time of the composite material is effectively prolonged;
(4) the functional nano kieselguhr loaded with the halloysite nanotube and the chitosan is used as one of the barrier anti-degradation slow-release materials, so that the barrier anti-degradation slow-release material is safe, non-toxic, good in biocompatibility, excellent in antibacterial effect and low in cost;
(5) the plant-based PA/PETG high-impact elastomer is used as one of the barrier and anti-degradation slow-release materials, so that the material is high in impact resistance, low in water absorption, wear-resistant, good in cohesiveness, acid-base resistant and excellent in surface printability; meanwhile, the elastomer has good compatibility with the PPC, and can accept the high filling amount of the PPC; in addition, when the elastomer is adopted, the problem of poor bonding force between PETG and PA11 is solved by modifying the elastomer, so that the elastomer is generated;
(6) in the preparation process of the elastomer, nanoparticles in the alloy elastomer have excellent dispersion and form uniform active nodes due to double-effect catalysis and dynamic crosslinking, and various polymer chains are interlaced and entangled to form a stable network, so that the final physical properties of the elastomer still have good performance even if more than 30% of regenerated resin is used.
(7) The scheme aims to realize the preparation of the biodegradable low-carbon composite material with high strength and durability, and overcomes the production problem in the industry.
Description of the figures
In order to more clearly illustrate the technical solutions in the embodiments or the prior art of the present application, the following briefly introduces diagrams needed to be used in the description of the embodiments or the prior art.
Table 1 is a component allocation ratio table of some of the examples;
table 2 is a group allocation ratio table of some of the examples
Table 3 is a table comparing the change in physical properties with the weight loss ratio for some of the examples;
table 4 is a table comparing the change in physical properties with the weight loss ratio for some of the examples;
table 5 is a table of initial tensile strength data distributions for some of the examples;
table 6 is a table of initial impact strength data distributions for some of the examples;
Detailed Description
The present invention will now be described in detail with reference to the following examples, in order to make the objects, features and advantages of the present invention more comprehensible. Several embodiments of the invention are given below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete:
the durable PLA/plant fiber low-carbon composite material and the preparation method thereof provided by the invention are described in detail as follows:
specifically, the invention provides a durable PLA/plant fiber low-carbon composite material which comprises the following components:
20-90 parts of modified biodegradable matrix resin;
0-50 parts of modified plant fiber;
1-5 parts of modified composite diatomite;
5-10 parts of high-impact PA11/PETG elastomer;
0-6 parts of modified seaweed powder;
1-5 parts of a crosslinking agent;
1-5 parts of a comprehensive auxiliary agent;
wherein the modified biodegradable matrix resin comprises a first modified resin and a second modified resin; the first modified resin is PPC, and the second modified resin comprises resin modified by one or more of PBAT, PCL, PLA, PBS, PBSA, PBST, PHB, PHA, PVA and PHBV;
further, the modified biodegradable matrix resin is preferably composed of modified PPC (polymethyl ethylene carbonate), modified PLA and modified PBS;
further, modified PPC, modified PLA and modified PBS
The proportion of the composite material is as follows:
10-15 parts of modified PPC;
5-54 parts of modified PLA;
0-30 parts of modified PBS.
Specifically, the modification process of the modified biodegradable matrix resin comprises the following steps:
solid-phase grafting reaction: respectively placing the modified biodegradable matrix resin in a vacuum drier for drying for 50-70 minutes, then adding the composite tourmaline additive and the grafting agent, carrying out ultraviolet irradiation, and mixing in a high-speed mixer to obtain the biodegradable matrix resin after solid phase grafting;
melt grafting reaction: respectively putting the solid-phase grafted biodegradable matrix resin into different high-speed mixers, and putting maleic anhydride and DCP for fully mixing;
wherein, the drying time of the modified biodegradable matrix resin is preferably 60 minutes in the modification process;
further, in the step of solid phase grafting reaction, the rotating speed of the high-speed mixer is 1000-1300 rpm, and the mixing time is 25-35 minutes
Furthermore, in the solid phase grafting reaction, the mixing speed of a high-speed machine is preferably 1200 revolutions per minute, and the time is preferably 30 minutes;
further, the proportion of maleic anhydride was 1% and the proportion of DCP was 0.05%.
Specifically, the modification process of the modified plant fiber or the modified seaweed powder comprises the following steps:
a1, putting the plant protomer into a vacuum rotary heating drier, and stirring and drying for 1-2 hours at 85-100 ℃;
a2, introducing oxygen gas flow, opening an ion source in a vacuum drier, and carrying out plasma treatment for 3-6 minutes while stirring;
a3, surface treatment of the first layer: spraying stearic acid and acetic anhydride under ultraviolet irradiation, and then carrying out illumination for about 5-10 minutes while stirring;
a4, surface treatment of the second layer: spraying stearic acid coupling agent, and stirring for 3-5 minutes under the irradiation of an ultraviolet lamp;
a5, surface treatment of the third layer: spraying PVA water solution and cross-linking agent, and stirring for 3-5 min under the irradiation of ultraviolet lamp.
Further, the plant protomer comprises one or more of bamboo fiber, straw MAI fiber, sisal fiber, kenaf fiber, rice straw fiber, rice hull powder or microalgae powder;
wherein, when the number of the plant prototypes is more than one, the modification processes of different plant prototypes are independently carried out;
further, in step a3, the stearic acid coupling agent accounts for 1% of the mass of the phytoplasma; acetic anhydride accounts for 1% of the mass of the phytoplasma.
Further, in step a5, the concentration of the PVA aqueous solution is preferably 5%; the cross-linking agent is preferably glyoxal and the stirring time is preferably 5 minutes.
Specifically, the modification process of the modified composite diatomite comprises the following steps:
b1, adding halloysite, a silane coupling agent, epoxidized soybean oil and stearic acid into a high-speed mixer, and stirring at a high speed, mixing and activating;
b2, further adding an antioxidant 1010, an antioxidant 168 and chitosan into the mixture obtained in step B2, and stirring and mixing to obtain casing polysaccharide intercalation halloysite;
b3, feeding the perianoglycan intercalation halloysite into a kneader, adding dopamine, PVA resin and kieselguhr, and mixing for 5-10 minutes at 90-130 ℃;
and B4, putting the mixture obtained in the step B3 into a double-screw granulator, and extruding and granulating at the temperature of 120-160 ℃.
Further, in the step B1, the components are respectively in parts by mass: 100 parts of halloysite, 1 part of silane coupling agent, 1 part of epoxidized soybean oil and 1 part of stearic acid;
in step B2, the components are, in parts by mass:
1010 parts of antioxidant, 10 parts; antioxidant 168, 10 parts; 30 parts of chitosan;
in step B3, the components are, in parts by mass: 1 part of dopamine, 5 parts of PVA resin and 300 parts of diatomite.
Further, the silane coupling agent is KH 570; in step B1, the stirring speed of the high-speed mixer is preferably 1000rpm, and the stirring time is preferably 30 minutes.
Specifically, the preparation of the high impact PA11/PETG elastomer comprises the following steps:
c1, mixing PA11, glycerol, formamide and a benzene sulfonamide plasticizer in a high-speed mixer for 30-60 minutes at a high speed, and then standing for later use;
c2, placing PETG, epoxy chain extender (ADR 4468), PPC and polyethylene glycol in another high-speed mixer, and mixing for 30-50 minutes at high speed;
c3, mixing the mixture obtained after the standing in the step C1 with the mixture obtained in the step C2, adding DCP (dicumyl peroxide) and GMA (glycidyl methacrylate), and mixing for 10-15 minutes;
c4, putting the uniformly mixed mixture obtained in the step C3 into a double-screw extruder for compatibilization grafting reaction; the extrusion granulation temperature is 160-190 ℃, and the high impact PA11/PETG elastomer is obtained.
Further, in step C1, the preferred ratios of the components are: PA11, 85%; 3% of glycerol; formamide, 2%; benzenesulfonamide plasticizer, 7%; the standing time is preferably 6 hours;
further, in step C2, the ratio of each component is: PETG, 90%; epoxy chain extender (ADR 4468), 1%; PPC, 5%; 4% of polyethylene glycol;
further, in the step C3, the ratio of the mixture in the step C1 to the mixture in the step C2 is 3:7, and the DCP and the GMA respectively account for 0.1% and 3% of the mass of the mixture after mixing in the step C3.
Specifically, the cross-linking agent consists of superfine barium sulfate, water-resistant agent carbodiimide and MDI (diphenyl methane diisocyanate) (cross-linking agent);
further, the proportion of each component of the cross-linking agent is preferably as follows: ultra-fine barium sulfate: water repellent carbodiimide: MDI =2:2: 1.
Specifically, the comprehensive assistant consists of calcium stearate, PE wax and an antioxidant 1010;
further, the proportion of each component of the comprehensive auxiliary agent is preferably as follows: calcium stearate: PE wax: antioxidant 1010=4-6:2-4: 1-3.
Further, the composition of the composite material is preferably:
37 parts of modified biodegradable matrix resin;
46 parts of modified plant fiber;
4 parts of modified composite diatomite;
high impact PA11/PETG elastomer, 8 parts;
3 parts of a crosslinking agent;
2 parts of comprehensive auxiliary agent.
The invention also provides a preparation method for preparing the durable PLA/plant fiber low-carbon composite material, which comprises the following steps:
putting the components in parts by proportion into a high mixing machine for mixing, feeding the uniformly mixed mixture into a double-screw extruder for micro-crosslinking reaction granulation, wherein the extrusion temperature is 160-;
further, in the above method, the rotation speed of the screw is preferably 120 rpm.
The following will be further discussed from specific examples:
example 1
The embodiment provides a carbon biodegradable green composite material, which comprises the following components:
X-PLA (54%) + X-PBS (29%) + X-PPC (15%) + Synthesis adjuvant Mix (2%);
wherein X-PLA, X-PBS and X-PPC respectively refer to modified PLA, modified PBS and modified PPC, and MIX refers to a comprehensive auxiliary agent;
the preparation method comprises the following steps:
(1) firstly, respectively placing three resins of PLA, PBS and PPC into a rotary vacuum dryer for drying for 60 minutes, then adding a composite tourmaline auxiliary agent and a grafting agent, turning on 4 UV lamps (total 100W) on a dryer cover, and mixing at high speed (1200 rpm) for 30 minutes to complete the solid-phase grafting reaction of the first stage;
(2) respectively putting the main raw materials (PLA, PBS and PPC after solid phase grafting) and the auxiliary agent into three different high-speed mixing machines for fully mixing;
a. PLA +1% MAH (maleic anhydride) +0.05% DCP;
b. PBS +1% MAH (maleic anhydride) +0.05% DCP;
c. PPC +1% MAH (maleic anhydride) +0.05% DCP;
after mixing for 15 minutes, respectively feeding the materials into a kneading machine, and then feeding the materials into a double-screw extruder to perform melt grafting reaction and granulation to obtain three graft resins of X-PLA, X-PBS, X-PPC and the like.
(3) The three grafted resins and the comprehensive assistant (Mix) are mixed in a high-speed mixer according to the formula proportion (15 minutes), then fed into a parallel double-screw extruder to perform dynamic micro-crosslinking reaction (the extrusion temperature is 160-plus-energy 180 ℃, the screw rotating speed is 120rpm), and the low-carbon biodegradable green composite material is obtained through granulation.
The material is suitable for manufacturing injection molding parts, has excellent physical strength and high surface activity, and the injection molded parts are easy to spray water-based paint or perform surface treatment on the appearance of imitation metal.
Comparative example 1
The embodiment provides a carbon biodegradable green composite material, which comprises the following components:
PLA (54%) + PBS (29%) + PPC (15%) + Synthesis adjuvant Mix (2%);
the preparation method comprises the following steps:
(1) vacuum dehumidification and drying of resin:
firstly, placing three resins of PLA, PBS and PPC into a rotary vacuum drier respectively to dry for 60 minutes;
(2) putting the main raw materials (PLA, PBS, PPC) and 2% of auxiliary agent (Mix) into a high-speed mixer for fully mixing;
(3) and after 15 minutes of mixing, feeding the mixture into a kneading machine, and feeding the mixture into a double-screw extruder for melt extrusion granulation. (the extrusion temperature is 160-.
Example 2
The embodiment provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, wherein the durable PLA/plant fiber low-carbon composite material comprises the following components:
X-PLA (35%), + X-PPC (10%), + t-rice straw fiber (20%), + t-rice hull powder (20%), + general diatomite (4%), + cross-linking agent CL (3%), + t-seaweed powder (6%), + comprehensive assistant Mix (2%);
wherein the t-rice straw fiber is modified rice straw fiber, and the explanation is referred to in the subsequent writing method; CL is a cross-linking agent;
the preparation method comprises the following steps:
(1) the modified biodegradable matrix resin is modified by a two-stage composite grafting method, and the specific method can refer to example 1;
(2) preparation of modified plant fibers
A1, taking rice straw fibers and rice hull powder, respectively putting into a vacuum rotary heating dryer, and stirring and drying for 1-2 hours at 80-100 ℃;
a2, introducing oxygen gas flow, turning on an ion source in a vacuum drier, stirring while performing plasma treatment for 3-6 minutes,
a3, after plasma treatment, turning on a UV light source on the inner side of an inner upper cover, spraying stearic acid (1% of the weight of the fiber) and acetic anhydride (1% of the weight of the fiber), and then carrying out illumination for about 5-10 minutes while stirring, wherein the first layer is surface treatment;
a4, spraying stearic acid coupling agent (accounting for 1 percent of the total weight of the fiber), stirring and UV irradiating for 3-5 minutes, and performing surface treatment on the second layer;
a5, the final layer was surface treated by spraying an aqueous PVA solution (5% strength) and a crosslinking agent (glyoxal) and UV-irradiation for 5 minutes with stirring.
(3) The prepared components are put into a high-speed mixer according to the formula and mixed (low-speed mixing is carried out for 3 minutes, high-speed mixing is carried out for 5 minutes, and then low-speed mixing is carried out for 3 minutes); and finally, feeding the uniformly mixed ingredients into a double-screw extruder for micro-crosslinking reaction granulation (the extrusion temperature is 160-.
Comparative example 2
The embodiment provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, wherein the durable PLA/plant fiber low-carbon composite material comprises the following components:
X-PLA (35%) + X-PPC (10%) + common rice straw fiber (20%) + common rice hull powder (20%) + common diatomite (4%) + cross-linking agent CL (3%) + common seaweed meal (6%) + comprehensive assistant Mix (2%);
the preparation method comprises the following steps:
(1) the modified biodegradable matrix resin is modified by a two-stage grafting method, and the specific method can refer to example 1;
(2) respectively putting the rice straw fiber and the rice hull powder into a vacuum rotary heating dryer, and stirring and drying for 1-2 hours at 80-100 ℃;
(3) the prepared components are put into a high-speed mixer according to the formula and mixed (low-speed mixing is carried out for 3 minutes, high-speed mixing is carried out for 5 minutes, and then low-speed mixing is carried out for 3 minutes); and finally, feeding the uniformly mixed ingredients into a double-screw extruder for micro-crosslinking reaction granulation (the extrusion temperature is 160-.
Example 3
The embodiment provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, wherein the durable PLA/plant fiber low-carbon composite material comprises the following components:
X-PLA (22%) + X-PPC (10%) + X-PBS (5%) + t-straw fiber (20%) + t-rice hull powder (20%) + high impact PA11/PETG elastomer (8%) + modified diatomaceous earth (HINS-CD) (4%) + cross-linking agent CL (3%) + t-seaweed powder (6%) + comprehensive adjuvant Mix (2%);
the preparation method comprises the following steps:
(1) the modified biodegradable matrix resin is modified by a two-stage grafting method, and the specific method can refer to example 1;
(2) the modified plant fiber is prepared by the specific method as shown in example 2;
(3) preparation of modified diatomaceous Earth
B1, placing 100 parts of halloysite into a high-speed mixer, adding 1 part of silane coupling agent (KH 570), and adding 1 part of epoxidized soybean oil (EBO) and 1 part of stearic acid; then starting high-speed stirring (1000 rpm) for 30 minutes to activate the mixture;
b2, adding 10 parts of antioxidant 1010, 10 parts of antioxidant 168 and 30 parts of chitosan, and mixing for 15-30 minutes to complete the peridium chitosan intercalation halloysite;
b3, feeding the chitosan intercalated halloysite in the step B2 into a kneader, and adding 1 part of dopamine, 5 parts of PVA resin and 300 parts of diatomite. Mixing for 5-10 minutes at 90-130 ℃;
b4, putting the mixture obtained in the step B3 into a double-screw granulator for modification granulation of diatomite; the extrusion temperature of the granulator is 120-160 ℃.
(4) Preparation of high impact PA11/PETG elastomer
C1, mixing 85% of PA11, 3% of glycerin, 2% of formamide and 7% of benzenesulfonamide plasticizer in a high-speed mixer for 30-60 minutes, and then standing for 6 hours;
c2, placing 90% of PETG, 1% of epoxy chain extender and 5% of PPC,4% of polyethylene glycol (PEG 2000) in another high-speed mixing machine, and mixing at high speed for 30 minutes;
and C3, taking 30 kg of the mixture obtained in the step C1 after standing for 6 hours, pouring into 70 kg of the mixture obtained in the step C2 (total 100 kg), adding 0.1% of DCP and 3% of GMA, and mixing for 10 minutes.
C4, feeding the uniformly mixed material obtained in the step C3 into a double-screw extruder for compatibilization grafting reaction. The extrusion granulation temperature is 160-190 ℃, so that the high impact PA11/PETG alloy elastomer is obtained.
(5) The prepared components are put into a high-speed mixer according to the formula and mixed (low-speed mixing is carried out for 3 minutes, high-speed mixing is carried out for 5 minutes, and then low-speed mixing is carried out for 3 minutes); and finally, feeding the uniformly mixed ingredients into a double-screw extruder for micro-crosslinking reaction granulation (the extrusion temperature is 160-.
Example 4
The embodiment provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, wherein the durable PLA/plant fiber low-carbon composite material comprises the following components:
X-PLA (22%) + X-PPC (10%) + X-PBS (5%) + t-bamboo fiber (40%) + high impact PA11/PETG elastomer (8%) + modified diatomite (4%) + cross-linking agent (3%) + t-seaweed meal (6%) + comprehensive adjuvant Mix (2%);
the preparation method specifically comprises the following steps:
(1) the modified biodegradable matrix resin is modified by a two-stage grafting method, and the specific method can refer to example 1;
(2) the modified plant fiber is prepared by the specific method as shown in example 2;
(3) the modified diatomite is prepared by the specific method according to the embodiment 3;
(4) the preparation of high impact PA11/PETG elastomer can be carried out by the specific method in example 3;
(5) the prepared components are put into a high-speed mixer according to the formula and mixed (low-speed mixing is carried out for 3 minutes, high-speed mixing is carried out for 5 minutes, and then low-speed mixing is carried out for 3 minutes); and finally, feeding the uniformly mixed ingredients into a double-screw extruder for micro-crosslinking reaction granulation (the extrusion temperature is 160-.
Example 5
The embodiment provides a durable PLA/plant fiber low-carbon composite material and a preparation method thereof, wherein the durable PLA/plant fiber low-carbon composite material comprises the following components:
X-PLA (5%) + X-PPC (10%) + X-PBS (15%) + t-straw fibre (20%) + t-rice hull powder (20%) + t-bamboo fibre (7%) + high impact PA11/PETG elastomer (8%) + modified diatomaceous earth (HINs-CD) (4%) + cross-linking agent CL (3%) + t-seaweed powder (6%) + comprehensive adjuvant Mix (2%);
(1) the modified biodegradable matrix resin is modified by a two-stage grafting method, and the specific method can refer to example 1;
(2) the modified plant fiber is prepared by the specific method as shown in example 2;
(3) the modified diatomite is prepared by the specific method according to the embodiment 3;
(4) the high impact PA11/PETG elastomer is prepared by the specific method which can refer to the embodiment 3;
(5) the prepared components are put into a high-speed mixer according to the formula and mixed (low-speed mixing is carried out for 3 minutes, high-speed mixing is carried out for 5 minutes, and then low-speed mixing is carried out for 3 minutes); finally, the evenly mixed ingredients are fed into a double-screw extruder for micro-crosslinking reaction granulation (the extrusion temperature is 160-190 ℃, and the screw rotation speed is 120 rpm).
In the technical scheme provided by the invention, the polypropylene carbonate (PPC) is adopted and is a biodegradable material, although the PPC is a completely degradable material with no toxicity and odor and good barrier property, the PPC has the problems of low mechanical property, poor thermal property, large brittleness, narrow processing temperature range , poor compatibility with other polymers (PLA, PBS, PBAT, PCL and the like) and the like, so the PPC is modified firstly to be effectively used; so the modified biodegradable matrix resin is modified by a two-stage composite grafting method;
furthermore, the invention emphasizes and controls the cost of raw materials, simultaneously considers the utilization of wastes, and inherits the aim of environmental protection, so that some plant fibers are adopted as one of the raw materials, and the characteristics of the plant fibers are utilized to enhance the composite material provided by the invention, but the compatibility between the biodegradable matrix resin and the plant fibers is also a big problem, so the scheme performs three surface treatments on the plant fibers and also modifies the plant fibers;
furthermore, the traditional biodegradable materials generally have the problem of service life, and no better solution is provided; according to the invention, through direct (quick release) and indirect (long-acting slow release) delaying and blocking means, the biodegradable polymer has excellent characteristics of efficient hydrolysis resistance, aging resistance, seepage resistance, cracking resistance and the like, so that the durability is greatly improved, and the biodegradable polymer has a wider application range;
furthermore, the first blocking anti-degradation slow-release material applied in the invention is modified diatomite, and further is functional nano diatomite loaded with halloysite nanotubes and chitosan; the halloysite nanotube is used as natural nano-clay in nature, is a natural one-dimensional nanotube, and has active hydroxy acids on the inner surface and the outer surface, so that surface modification or introduction of functional groups is easy to perform; in addition, the chitosan is selected as a natural degradable polymer, so that the chitosan has good biocompatibility and has an antibacterial effect; the diatomite can improve the heat resistance and the mechanical strength, and can also smoothen the surface of the material (reduce surface convex points and floating fibers) and facilitate printing; thus, the composite material provided by the invention can integrate the characteristics; however, it is not easy to synthesize the modified diatomite by combining the above materials, and the scheme is to modify and activate the halloysite nanotube, connect the antioxidant and the anti-hydrolysis agent, perform the densification intercalation on the chitosan, and perform the secondary melt extrusion intercalation on the intercalation and the modified diatomite (PVA modified) by using the cross-linking agent.
Furthermore, the second barrier anti-degradation slow-release material applied in the invention is a high-impact PA11/PETG elastomer, and PETG (polyethylene terephthalate glycol-1, 4-cyclohexanedimethanol ester) is PET copolymer resin, and the material has the advantages of high transparency, good toughness, good weather resistance, easy processing and is a well-known environment-friendly material. The invention selects PETG and plant-based nylon PA11 to be blended and crosslinked to form the anti-fatigue cracking elastomer, which has the following advantages:
(1) the paint has the advantages of high impact resistance, (2) low water absorption, (3) wear resistance, (4) good cohesiveness, (5) acid and alkali resistance, and (6) excellent surface printability; the elastomer has the other characteristics that the elastomer has very good compatibility with the PPC and can accept high filling amount of the PPC; however, the PETG and the PA11 have poor bonding force, and cannot be comprehensively applied simply, so the scheme further adopts the scheme that GMA is grafted after PA11 is softened, and the GMA and the PETG undergo chain extension reaction and are finally melted and co-extruded to form the compatible high-impact elastomer.
Furthermore, the double-effect catalysis and dynamic crosslinking are utilized to enable the nano particles in the alloy elastomer to have excellent dispersion and form uniform active nodes, various polymer chains are interlaced and entangled to form a stable network, and therefore even if more than 30% of regenerated resin is used, the final physical properties still have good performance.
Further analysis was performed from the final experimental results of the examples as follows:
referring to fig. 3 specifically, comparing comparative example 1 with example 1, the weight loss ratio of example 1 is greatly different from that of comparative example 1, so that the present invention can obviously prolong the service life in practical application by modifying the biodegradable matrix resin.
Referring to fig. 4 specifically, comparing comparative example 2 with example 2, it can be seen that each parameter in example 2 is significantly better than comparative example 2, and there is a large difference between tensile strength, elongation at break and final weight loss ratio, so that the present scheme effectively improves the binding force between the plant and the polymer by further performing the activated grafting treatment on the plant fiber, and further significantly improves each physical property of the material.
Referring to fig. 4, comparing examples 3 to 5 with comparative example 2, and examples 3 to 5, after adding two sustained-release anti-degradation blocking agents, the physical properties of the composite material are further improved, and specifically, the weight loss ratio of example 4 can be compared with that of comparative example 2, wherein the weight loss ratio of comparative example after 30 days is-53.6%, and the weight loss ratio of example 4 after 30 days is only-14.3%, which is different by more than two times, which is very considerable in prolonging the service life of the material.
Further, referring to fig. 5-6, by performing this experiment on the material, the stability of the comparative material, as compared to comparative example 2, example 2 and example 4, can be obtained from the results of multiple experiments, and not only the original data of example 2 and example 4 is better than that of comparative example 2, but also the stability of example 2 is better than that of comparative example 2, thereby further proving that the two "multi-stage multiple graft" in this scheme makes the bonding force between the resin and the plant fiber very uniform and stable in the present application.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present application are intended to be included within the scope of the present application.
Claims (18)
1. A durable PLA/plant fiber low-carbon composite material is characterized in that: the composite material comprises the following components:
20-90 parts of modified biodegradable matrix resin;
0-50 parts of modified plant fiber;
1-5 parts of modified composite diatomite;
5-10 parts of high-impact PA11/PETG elastomer;
0-6 parts of modified seaweed powder
1-5 parts of a crosslinking agent;
1-5 parts of a comprehensive auxiliary agent;
the modified biodegradable matrix resin comprises a first modified resin and a second modified resin;
the first modified resin is PPC (poly propylene carbonate), and the second modified resin comprises one or more modified resins of PBAT, PCL, PLA, PBS, PBSA, PBST, PHB, PHA, PVA and PHBV.
2. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the modified biodegradable matrix resin consists of modified PPC, modified PLA and modified PBS.
3. The durable PLA/plant fiber low carbon composite of claim 2, wherein: the proportion of the modified PPC, the modified PLA and the modified PBS in the composite material is as follows:
10-15 parts of modified PPC;
5-54 parts of modified PLA;
0-30 parts of modified PBS.
4. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the modification process of the modified biodegradable matrix resin comprises the following steps:
solid-phase grafting reaction: respectively placing the modified biodegradable matrix resin in a vacuum drier for drying for 50-70 minutes, then adding the composite tourmaline additive and the grafting agent, carrying out ultraviolet irradiation, and adding into a high-speed mixer for mixing to obtain the biodegradable matrix resin after solid phase grafting;
melt grafting reaction: respectively putting the solid-phase grafted biodegradable matrix resin into different high-speed mixers, and putting maleic anhydride and DCP for fully mixing.
5. The durable PLA/plant fiber low carbon composite of claim 3, wherein: in the solid phase grafting reaction step, the rotation speed of the high-speed mixer is 1000-1300 rpm, and the mixing time is 25-35 minutes.
6. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the modification process of the modified plant fiber or the modified seaweed powder comprises the following steps:
a1, putting the plant protomer into a vacuum rotary heating drier, and stirring and drying for 1-2 hours at 80-100 ℃;
a2, introducing oxygen gas flow, opening an ion source in a vacuum drier, and carrying out plasma treatment for 3-6 minutes while stirring;
a3, surface treatment of the first layer: spraying stearic acid and acetic anhydride under ultraviolet irradiation, and then carrying out illumination for about 5-10 minutes while stirring;
a4, second layer surface treatment: spraying stearic acid coupling agent, and stirring for 3-5 minutes under the irradiation of an ultraviolet lamp;
a5, surface treatment of the third layer: spraying PVA water solution and cross-linking agent, and stirring for 3-5 min under the irradiation of ultraviolet lamp.
7. The durable PLA/plant fiber low carbon composite of claim 5, wherein: the plant protomer comprises one or more of bamboo fiber, MAI straw fiber, sisal fiber, kenaf fiber, rice straw fiber, rice hull powder or microalgae powder;
when the plant protomer is more than one, the modification process of different plant protomers is separately carried out.
8. The durable PLA/plant fiber low carbon composite of claim 5, wherein: in step a3, the stearic acid coupling agent comprises 1% by mass of the phytoplasma; acetic anhydride represents 1% of the mass of the phytoplasma.
9. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the modification process of the modified composite diatomite comprises the following steps:
b1, adding halloysite, a silane coupling agent, epoxidized soybean oil and stearic acid into a high-speed mixer, and stirring at a high speed, mixing and activating;
b2, further adding an antioxidant 1010, an antioxidant 168 and chitosan into the mixture obtained in the step B2, and stirring and mixing to obtain peridium chitosan intercalated halloysite;
b3, feeding the perianoglycan intercalation halloysite into a kneader, adding dopamine, PVA resin and kieselguhr, and mixing for 5-10 minutes at 90-130 ℃;
and B4, putting the mixture obtained in the step B3 into a double-screw granulator, and extruding and granulating at the temperature of 120-160 ℃.
10. The durable PLA/plant fiber low carbon composite of claim 8, wherein:
in step B1, the components are, in parts by mass: 100 parts of halloysite, 1 part of silane coupling agent, 1 part of epoxidized soybean oil and 1 part of stearic acid;
in step B2, the components are, in parts by mass:
1010 parts of antioxidant, 10 parts; antioxidant 168, 10 parts; 30 parts of chitosan;
in step B3, the components are, in parts by mass: 1 part of dopamine, 5 parts of PVA resin and 300 parts of diatomite.
11. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the preparation of the high impact PA11/PETG elastomer comprises the following steps:
c1, mixing PA11, glycerol, formamide and benzene sulfonamide plasticizer in a high-speed mixer for 30-60 minutes at a high speed, and standing for later use;
c2, placing PETG, epoxy chain extender (ADR 4468), PPC and polyethylene glycol in another high-speed mixer, and mixing for 30-50 minutes at high speed;
c3, mixing the mixture obtained after the standing in the step C1 with the mixture obtained in the step C2, adding DCP (dicumyl peroxide) and GMA (glycidyl methacrylate), and mixing for 10-15 minutes;
c4, putting the uniformly mixed mixture obtained in the step C3 into a double-screw extruder for compatibilization grafting reaction; the extrusion granulation temperature is 160-190 ℃, and the high impact PA11/PETG elastomer is obtained.
12. The durable PLA/plant fiber low carbon composite of claim 10, wherein: in step C1, the ratio of each component is: PA11, 85%; 3% of glycerol; formamide, 2%; benzenesulfonamide plasticizer, 7%; standing for 6 hours;
in step C2, the ratio of each component is: PETG, 90%; epoxy chain extender (ADR 4468), 1%; PPC, 5%; 4% of polyethylene glycol;
in the step C3, the ratio of the mixture in the step C1 to the mixture in the step C2 is 3:7, and the DCP and the GMA respectively account for 0.1% and 3% of the mass of the mixture mixed in the step C3.
13. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the cross-linking agent consists of superfine barium sulfate, water-resistant agent carbodiimide and MDI (diphenyl-methane diisocyanate) which is a cross-linking agent.
14. The durable PLA/plant fiber low carbon composite of claim 12, wherein: the cross-linking agent comprises the following components in percentage by weight: ultra-fine barium sulfate: water repellent carbodiimide: MDI =2:2: 1.
15. The durable PLA/plant fiber low carbon composite of claim 1, wherein: the comprehensive assistant consists of calcium stearate, PE wax and an antioxidant 1010.
16. The durable PLA/plant fiber low carbon composite of claim 14, wherein: the comprehensive auxiliary agent comprises the following components in percentage by weight: calcium stearate: PE wax: antioxidant 1010=4-6:2-4: 1-3.
17. The durable PLA/plant fiber low carbon composite of any one of claims 1-16, wherein: the composite material comprises the following components:
37 parts of modified biodegradable matrix resin;
46 parts of modified plant fiber;
4 parts of modified composite diatomite;
high impact PA11/PETG elastomer, 8 parts;
3 parts of a crosslinking agent;
2 parts of comprehensive auxiliary agent.
18. A preparation method of a durable PLA/plant fiber low-carbon composite material is characterized by comprising the following steps: for the preparation of a durable PLA/plant fiber low carbon composite as claimed in any one of claims 1-17, comprising the steps of:
putting the components in parts by proportion into a high mixing machine for mixing, feeding the uniformly mixed mixture into a double-screw extruder for micro-crosslinking reaction granulation, wherein the extrusion temperature is 160-190 ℃, and obtaining the durable PLA/plant fiber low-carbon composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210546273.0A CN115093667A (en) | 2022-05-20 | 2022-05-20 | Durable PLA/plant fiber low-carbon composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210546273.0A CN115093667A (en) | 2022-05-20 | 2022-05-20 | Durable PLA/plant fiber low-carbon composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115093667A true CN115093667A (en) | 2022-09-23 |
Family
ID=83289187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210546273.0A Pending CN115093667A (en) | 2022-05-20 | 2022-05-20 | Durable PLA/plant fiber low-carbon composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115093667A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090018235A1 (en) * | 2006-02-24 | 2009-01-15 | Phb Industrial S.A. | Environmentally degradable polymeric composition and process for obtaining an environmentally degradable polymeric composition |
| CN110655769A (en) * | 2019-11-08 | 2020-01-07 | 佰信(福建)新材料科技有限公司 | High-toughness fully-degradable composite material |
| CN112980158A (en) * | 2021-03-16 | 2021-06-18 | 晋江市新迪新材料科技有限公司 | Bamboo-based fiber reinforced full-biodegradable composite material |
-
2022
- 2022-05-20 CN CN202210546273.0A patent/CN115093667A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090018235A1 (en) * | 2006-02-24 | 2009-01-15 | Phb Industrial S.A. | Environmentally degradable polymeric composition and process for obtaining an environmentally degradable polymeric composition |
| CN110655769A (en) * | 2019-11-08 | 2020-01-07 | 佰信(福建)新材料科技有限公司 | High-toughness fully-degradable composite material |
| CN112980158A (en) * | 2021-03-16 | 2021-06-18 | 晋江市新迪新材料科技有限公司 | Bamboo-based fiber reinforced full-biodegradable composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101914294B (en) | Paper-imitating biodegradable resin and preparation method | |
| CN110358264B (en) | Bio-based environment-friendly packaging bag and preparation method thereof | |
| CN105504363A (en) | Starch and plant fiber composite biodegradable polyester film-blowing grade resin and preparation method | |
| CA2900596C (en) | Microstructured composite material, method for the production thereof, moulded articles made hereof and also purposes of use | |
| CN111286168A (en) | Biodegradable polyester/cellulose composite blown film material and preparation method thereof | |
| CN107955244B (en) | Functional polyethylene resin with antibacterial performance and preparation method thereof | |
| US6863971B2 (en) | Strong durable low cost composite materials made from treated cellulose and plastic | |
| TW201538529A (en) | Starch-group biodegradable composite material and its preparation method | |
| CN1793229A (en) | Complete degradable material with polyalctic as carrier and preparation process thereof | |
| CN105504704A (en) | Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method | |
| EP1383824B1 (en) | Composite materials made from treated cellulose and plastic | |
| CN1712436A (en) | Aliphatic polyester/starch/clay ternary degradable resin and production thereof | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN115093667A (en) | Durable PLA/plant fiber low-carbon composite material and preparation method thereof | |
| CN112812518A (en) | Thermoplastic biodegradable plastic and preparation method thereof | |
| CN104558700B (en) | Preparing method of bioplastic master batch | |
| CN110628233A (en) | Cross-linking reaction extruded wood-plastic profile and preparation method thereof | |
| KR101507960B1 (en) | A bioplastic composition comprising glass bead with improved flowability for injecting and the method thereof | |
| KR101208107B1 (en) | Manufacturing method of plastic for car interior material using biomass pellet and thereof | |
| CN115368720A (en) | Degradable polymer nano composite material and preparation method thereof | |
| CN1047783C (en) | Reversible cross-linked starch resin compound and its preparation method | |
| US20020171162A1 (en) | Strong durable low cost composite materials | |
| CN1135550A (en) | Degraded leather-imitation and production method and application thereof | |
| CN114044961B (en) | Photodegradable environment-friendly plastic packaging bag and production process thereof | |
| TWI792777B (en) | Clothing fiber wood and preparation method thereof |
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 |