CN116478512A - Biodegradable biomass thermoplastic blending composite material, product and preparation method thereof - Google Patents
Biodegradable biomass thermoplastic blending composite material, product and preparation method thereof Download PDFInfo
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- CN116478512A CN116478512A CN202310416141.0A CN202310416141A CN116478512A CN 116478512 A CN116478512 A CN 116478512A CN 202310416141 A CN202310416141 A CN 202310416141A CN 116478512 A CN116478512 A CN 116478512A
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- biodegradable
- biomass
- blending composite
- thermoplastic
- methylmorpholine
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- 239000002028 Biomass Substances 0.000 title claims abstract description 91
- 238000002156 mixing Methods 0.000 title claims abstract description 88
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 73
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 69
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920002472 Starch Polymers 0.000 claims abstract description 11
- 239000008107 starch Substances 0.000 claims abstract description 11
- 235000019698 starch Nutrition 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000001913 cellulose Substances 0.000 claims abstract description 7
- 229920002678 cellulose Polymers 0.000 claims abstract description 7
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 7
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 244000061456 Solanum tuberosum Species 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 240000006394 Sorghum bicolor Species 0.000 claims description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 244000098338 Triticum aestivum Species 0.000 claims 1
- 238000010104 thermoplastic forming Methods 0.000 claims 1
- 238000009757 thermoplastic moulding Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 238000001746 injection moulding Methods 0.000 description 15
- -1 polybutylene terephthalate-adipate Polymers 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 241000209140 Triticum Species 0.000 description 7
- 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 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 244000082204 Phyllostachys viridis Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 235000012015 potatoes Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- WAZPLXZGZWWXDQ-UHFFFAOYSA-N 4-methyl-4-oxidomorpholin-4-ium;hydrate Chemical compound O.C[N+]1([O-])CCOCC1 WAZPLXZGZWWXDQ-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 240000004922 Vigna radiata Species 0.000 description 1
- 235000010721 Vigna radiata var radiata Nutrition 0.000 description 1
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 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 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a biodegradable biomass thermoplastic blending composite material, a product and a preparation method thereof. The invention relates to a biodegradable biomass thermoplastic blending composite material or product, which comprises 50-90% of biodegradable synthetic polymer and 10-50% of total amount of biomass material and N-methylmorpholine-N-oxide. The melting point of the biodegradable synthetic polymer is less than or equal to 140 ℃. The biomass material is one or more of starch material, cellulose material and protein material. The mass ratio of the biomass material to the N-methylmorpholine-N-oxide is 4:1-1:2. The preparation method adopts a melt mixing and melt molding method, the melt mixing temperature is less than or equal to 140 ℃, and the thermoplastic molding temperature is less than or equal to 140 ℃. The composite biomass biodegradable composite material can be biodegraded, has excellent mechanical properties, and the preparation method is simple and easy to implement.
Description
Technical Field
The invention relates to a biodegradable thermoplastic material, a product and a preparation method thereof, in particular to a biodegradable biomass thermoplastic blending composite material, a product and a preparation method thereof, belonging to the field of biodegradable polymer materials and products.
Background
With the progress of material science, the requirements on the material are not only reflected in the requirement that the material has good performance, but also the requirement that the material has good environmental protection property. Most of the traditional high polymer materials used at present are from petrochemical industry, although the performance is better, the traditional high polymer materials are mostly difficult to degrade in environment, and the environment is polluted for a long time by the residues after the traditional high polymer materials are used. Biodegradable synthetic polymers are an important application direction, but they tend to be costly, affecting their wide application and popularization. Biomass materials, such as starch materials, cellulose materials, protein materials, are naturally derived, renewable resources on earth, are cheap and abundant, can be completely biodegraded, but often have a large number of hydrogen bonds in and among molecules, and are often difficult to be formed into applicable products by hot melting. The biodegradable blending composite material which is formed by compounding biomass material and biodegradable synthetic polymer is an important direction of the development of biodegradable materials, but the realization of high performance and low cost is a direction of continuous efforts.
Disclosure of Invention
The invention aims to provide a biodegradable biomass thermoplastic blending composite material which can be biodegraded, has excellent mechanical properties and a simple and easy preparation method, a product and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows: the biodegradable biomass thermoplastic blending composite material or product comprises 50-90% of biodegradable synthetic polymer and 10-50% of total amount of biomass material and N-methylmorpholine-N-oxide.
The melting point of the biodegradable synthetic polymer in the biodegradable biomass thermoplastic blending composite material or product is less than or equal to 140 ℃.
The biomass material in the biodegradable biomass thermoplastic blending composite material or the product can be one or more of starch material, cellulose material and protein material.
The starch material in the biodegradable biomass thermoplastic blending composite material or the product can be one or more of rice, wheat, corn, sorghum and potato.
The mass ratio of the biomass material to the N-methylmorpholine-N-oxide in the biodegradable biomass thermoplastic blending composite material or the product is preferably 4:1-1:2.
The biodegradable biomass thermoplastic blending composite product is formed by thermoplastic processing.
The preparation method of the biodegradable biomass thermoplastic blending composite material or the product of the invention can be as follows: the method sequentially comprises the following steps of:
(1) Mixing a biodegradable synthetic polymer, a biomass material and an N-methylmorpholine-N-oxide liquid;
(2) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
The preparation method of the biodegradable biomass thermoplastic blending composite material or the product of the invention can also be as follows: the method sequentially comprises the following steps of:
(1) Mixing a biomass material with an N-methylmorpholine-N-oxide liquid;
(2) Solid state mixing with biodegradable synthetic polymer particles;
(3) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
For the preparation method of the biodegradable biomass thermoplastic blending composite material or the product, the content of the N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide liquid is more than or equal to 75 percent.
For the preparation method of the biodegradable biomass thermoplastic blending composite material or product, the melting and mixing temperature of a screw extruder is less than or equal to 140 ℃, and the thermoplastic molding temperature is less than or equal to 140 ℃.
The biomass thermoplastic material, the product and the preparation method thereof have the following remarkable advantages: (1) The N-methylmorpholine-N-oxide adopted by the invention is environment-friendly, and the biomass thermoplastic blending composite material and the product can be biodegraded, have excellent mechanical properties and low cost; (2) The preparation method of the biomass thermoplastic blending composite material or the product is simple, convenient and feasible, can thermoplastic and mold the product, and has simple molding method and low cost.
Detailed Description
The invention relates to a biodegradable biomass thermoplastic blending composite material or product, which comprises 50-90% of biodegradable synthetic polymer and 10-50% of total amount of biomass material and N-methylmorpholine-N-oxide.
The melting point of the biodegradable synthetic polymer in the biodegradable biomass thermoplastic blending composite material or product is less than or equal to 140 ℃. The biodegradable synthetic polymer may be polybutylene terephthalate-adipate, polybutylene succinate, polycaprolactone, etc.
The biomass material in the biodegradable biomass thermoplastic blending composite material or the product can be one or more of starch material, cellulose material and protein material. The term "one or more" as used herein means two or more.
The starch material in the biodegradable biomass thermoplastic blending composite material or the product of the invention refers to plant materials with organic components mainly including starch, and can be one or more of rice, wheat, corn, sorghum and potato. The potatoes can be potatoes, sweet potatoes, cassava and the like. The cellulose material is plant material with organic component mainly cellulose, such as cotton, wood powder, bamboo powder, bagasse, reed, corn stalk, grass, rice hull, walnut shell, etc. The protein material is plant material and animal fiber material with organic components mainly containing protein, such as beans (soybean, pea, mung bean, etc.), bean dregs, silk, wool, etc.
The mass ratio of the biomass material to the N-methylmorpholine-N-oxide in the biodegradable biomass thermoplastic blending composite material or the product is preferably 4:1-1:2, and is preferably 3:1-1:1. The biodegradable biomass thermoplastic blending composite material or product can contain starch plasticizer which is less than 1/3 of the mass of N-methylmorpholine-N-oxide, such as glycerol, triethanolamine, sorbitol, ionic liquid, … and the like. The biodegradable biomass thermoplastic blending composite material or product of the invention can also contain inorganic fillers such as calcium carbonate, talcum powder, montmorillonite, inorganic fiber, … and the like, and can also contain other biomass materials such as chitin (such as powder), animal fat, biomass derivatives, … and the like. The biodegradable biomass thermoplastic blending composite material of the invention can also contain other materials, for example, a proper amount of non-biodegradable synthetic polymer with viscosity flow temperature less than or equal to 140 ℃ is blended, and particularly, a proper amount of non-biodegradable elastomer material (such as ethylene-vinyl acetate copolymer, ethylene propylene rubber, polyurethane, butadiene rubber and other rubber and SBS and other thermoplastic elastomer) is blended in a thermoplastic manner so as to improve toughness; for example, fibers (such as polylactic acid fibers, polyamide fibers, polyester fibers and the like) of synthetic polymers (including biodegradable polymers) with viscous flow temperature more than or equal to 140 ℃ can be compounded to improve strength; for example, a proper amount of asphalt or other materials are blended; … …; etc. Those skilled in the art will appreciate that materials or products obtained by blending, compounding, etc. the biodegradable biomass thermoplastic blending composite material of the present invention with other materials are also within the scope of the present invention, and that materials or products obtained by such blending, compounding, etc. are also within the scope of the present invention because they are biomass thermoplastic blending composite materials composed of 50% -90% of biodegradable synthetic polymer and 10% -50% of the total amount of biomass material and N-methylmorpholine-N-oxide.
Of course, the biodegradable biomass thermoplastic blend composite materials or articles of the present invention may also contain various additives commonly used in thermoplastic polymer materials or articles (e.g., processing aids, compatibilizers, interface modifiers, …, etc.) or other additives (e.g., pigments, flame retardants, antimicrobial agents, …, etc.), which are well known to those skilled in the art, and are within the scope of the present invention.
The biodegradable biomass thermoplastic blending composite product is formed by thermoplastic processing.
The preparation method of the biodegradable biomass thermoplastic blending composite material or the product of the invention can be as follows: the method sequentially comprises the following steps of:
(1) Mixing a biodegradable synthetic polymer, a biomass material and an N-methylmorpholine-N-oxide liquid;
(2) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
The preparation method of the biodegradable biomass thermoplastic blending composite material or the product of the invention can also be as follows: the method sequentially comprises the following steps of:
(1) Mixing a biomass material with an N-methylmorpholine-N-oxide liquid;
(2) Solid state mixing with biodegradable synthetic polymer particles;
(3) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
Of course, other suitable methods of preparation may be employed for the biodegradable biomass thermoplastic blend composite or article of the present invention.
For the preparation method of the biodegradable biomass thermoplastic blending composite material or the product, the content of the N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide liquid is more than or equal to 75 percent. The N-methylmorpholine-N-oxide content in the N-methylmorpholine-N-oxide liquid is preferably not less than 80%, for example, the N-methylmorpholine-N-oxide liquid is N-methylmorpholine-N-oxide monohydrate. The N-methylmorpholine-N-oxide liquid may contain starch plasticizers such as glycerol, triethanolamine, sorbitol, ionic liquid, …, etc. less than 1/3 of the mass of N-methylmorpholine-N-oxide.
For the preparation method of the biodegradable biomass thermoplastic blending composite material or product, the melting and mixing temperature of the screw extruder is less than or equal to 140 ℃, and is preferably 100-130 ℃. Besides extrusion molding, the biodegradable biomass thermoplastic blending composite material can be molded into the biodegradable biomass thermoplastic blending composite product by adopting thermoplastic processing methods such as injection molding, pressing, calendaring and the like, wherein the thermoplastic molding temperature is less than or equal to 140 ℃.
Example 1
700g of polybutylene terephthalate-adipate and 90g of an aqueous N-methylmorpholine-N-oxide solution containing 13.5% of water were heated to 95℃and mixed, followed by mixing with 210g of bamboo powder and 10g of antioxidant 1010 at 95 ℃. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 8.1MPa and an elongation at break of 315% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Example 2
180g of wheat flour was mixed with 120g of N-methylmorpholine-N-oxide aqueous material containing 13.5% water and 10% glycerol by heating to 90℃and then with 700g of polybutylene terephthalate-adipate and 10g of antioxidant 1010. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 13.1MPa and an elongation at break of 840% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Example 3
280g of wheat flour was mixed with 120g of N-methylmorpholine-N-oxide aqueous material containing 13.5% of water and 10% of glycerol by heating to 90℃and then with 600g of polybutylene terephthalate-adipate and 10g of antioxidant 1010. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 7.5MPa and an elongation at break of 356% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Example 4
140g of wheat flour was mixed with 60g of N-methylmorpholine-N-oxide aqueous material containing 13.5% water and 10% glycerol by heating to 90℃and then with 800g of polybutylene terephthalate-adipate and 10g of antioxidant 1010. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 12.3MPa and an elongation at break of 472% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Example 5
120g of wheat flour, 60g of bamboo powder and 120g of N-methylmorpholine-N-oxide water containing 13.5% of water and 10% of glycerol are heated to 90 ℃ and mixed, and then 700g of polybutylene terephthalate-adipate and 10g of antioxidant 1010 are mixed. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 13.3MPa and an elongation at break of 765% after 24 hours under constant temperature and humidity at 50% relative humidity at 23 ℃.
Comparative example 1
700g of polybutylene terephthalate-adipate was mixed with 300g of bamboo powder, 10g of antioxidant 1010 at 95 ℃. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite comparative material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 7.2MPa and an elongation at break of 185% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Comparative example 2
300g of wheat flour was mixed with 700g of polybutylene terephthalate-adipate and 10g of antioxidant 1010 at 90 ℃. And then, carrying out melt blending extrusion on the materials at 120 ℃ through a double-screw extruder, cooling by cold air, and then delivering into a granulator for granulation to obtain the biodegradable biomass thermoplastic blending composite comparative material. The tensile bar obtained by injection molding at 120 ℃ by an injection molding machine has a tensile strength of 7.1MPa and an elongation at break of 290% after 24 hours at a constant temperature and a constant humidity at 50% relative humidity of 23 ℃.
Claims (10)
1. A biodegradable biomass thermoplastic blend composite material or article, characterized in that: comprises 50 to 90 percent of biodegradable synthetic polymer and 10 to 50 percent of the total amount of biomass material and N-methylmorpholine-N-oxide.
2. The biodegradable biomass thermoplastic blending composite or article according to claim 1, characterized in that: the melting point of the biodegradable synthetic polymer is less than or equal to 140 ℃.
3. The biodegradable biomass thermoplastic blending composite or article according to claim 1 or 2, characterized in that: the biomass material is one or more of starch material, cellulose material and protein material.
4. A biodegradable biomass thermoplastic blending composite or article according to any of claims 1 to 3, characterized in that: the starch material is one or more of rice, wheat, corn, sorghum and potato.
5. The biodegradable biomass thermoplastic blending composite or article according to any one of claims 1 to 4, characterized in that: the mass ratio of the biomass material to the N-methylmorpholine-N-oxide is 4:1-1:2.
6. The biodegradable biomass thermoplastic blending composite or article according to any one of claims 1 to 5, characterized in that: and (5) forming into an article by thermoplastic processing.
7. The method of preparing a biodegradable biomass thermoplastic blending composite or article according to any of claims 1 to 6, characterized in that: the method sequentially comprises the following steps of:
(1) Mixing a biodegradable synthetic polymer, a biomass material and an N-methylmorpholine-N-oxide liquid;
(2) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
8. The method of preparing a biodegradable biomass thermoplastic blending composite or article according to any of claims 1 to 6, characterized in that: the method sequentially comprises the following steps of:
(1) Mixing a biomass material with an N-methylmorpholine-N-oxide liquid;
(2) Solid state mixing with biodegradable synthetic polymer particles;
(3) And (3) adopting a screw extruder to melt and mix, extruding to obtain the biodegradable biomass thermoplastic blending composite material or extruding to obtain the biodegradable biomass thermoplastic blending composite product.
9. The method of making a biodegradable biomass thermoplastic blending composite or article according to claim 7 or 8, characterized in that: the content of the N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide liquid is more than or equal to 75 percent.
10. The method of preparing a biodegradable biomass thermoplastic blending composite or article according to any of claims 7 to 9, characterized in that: the melting mixing temperature of the screw extruder is less than or equal to 140 ℃, and the thermoplastic forming temperature is less than or equal to 140 ℃.
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