CN113881195A - Biodegradable resin composition and preparation method thereof - Google Patents
Biodegradable resin composition and preparation method thereof Download PDFInfo
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- CN113881195A CN113881195A CN202111157465.4A CN202111157465A CN113881195A CN 113881195 A CN113881195 A CN 113881195A CN 202111157465 A CN202111157465 A CN 202111157465A CN 113881195 A CN113881195 A CN 113881195A
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- biodegradable resin
- acrylate copolymer
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920005610 lignin Polymers 0.000 claims abstract description 59
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 38
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000002667 nucleating agent Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims description 29
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229920006238 degradable plastic Polymers 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 8
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims description 8
- JFJWVJAVVIQZRT-UHFFFAOYSA-N 2-phenyl-1,3-dihydropyrazole Chemical class C1C=CNN1C1=CC=CC=C1 JFJWVJAVVIQZRT-UHFFFAOYSA-N 0.000 claims description 7
- UZNDHCZORMBARB-UHFFFAOYSA-N 4-hydroxylauric acid Chemical compound CCCCCCCCC(O)CCC(O)=O UZNDHCZORMBARB-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical class N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 150000001893 coumarin derivatives Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000008048 phenylpyrazoles Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008188 pellet Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- OVARTXYXUGDZHU-UHFFFAOYSA-N 4-hydroxy-n-phenyldodecanamide Chemical compound CCCCCCCCC(O)CCC(=O)NC1=CC=CC=C1 OVARTXYXUGDZHU-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011155 wood-plastic composite Substances 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
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a preparation method of a biodegradable resin composition, wherein a production raw material formula comprises the following components in percentage by mass: 100 parts of a butanediol adipate-butanediol terephthalate copolymer, 15-30 parts of lignin powder, 5-15 parts of a methyl acrylate copolymer, 0.5-2 parts of an antioxidant, 0.5-7 parts of a chain extender and 0.1-1 part of a nucleating agent. The advantages are that: the biodegradable resin composition and the product have excellent mechanical property and transparency, simultaneously recover and utilize lignin, and have excellent biodegradation performance.
Description
Technical Field
The invention relates to the field of processing of high polymer materials, in particular to a production technology of a biodegradable material.
Background
The plastic shopping bag is a consumable article in daily life. In modern agricultural production, agricultural mulching films and vegetable greenhouse films are widely applied, especially in arid water-deficient areas. Traditional mulching films and greenhouse films are mostly produced by petroleum-based raw materials, such as polyethylene bags, biaxially oriented polypropylene bags and polystyrene. These types of materials take a very long time to decompose, do not decompose or degrade in the natural environment, produce "white pollution," and place a heavy burden on nature.
Biodegradable plastics refer to a class of microorganisms that exist in nature such as: plastics degraded by the action of bacteria, molds (fungi) and algae. Can be completely decomposed by environmental microorganisms after being discarded, and finally becomes inorganic to become a polymer material which is part of carbon cycle in nature.
Patent CN110373010A discloses a preparation method of a composite degradable plastic bag, which is characterized in that a degradable plastic bag is prepared by adding degradable plastic base stock, modified bamboo fiber, dioctyl phthalate and diamine, mixing and granulating and then extruding, and the product has excellent mechanical strength and better oil stain resistance, but the transparency of the product is greatly reduced, and the range limitation is realized when the product is used.
The lignin powder is one of the main raw materials of the wood-plastic composite material, and most of the lignin powder generated every year is discarded, thereby causing serious environmental pollution and social problems. If the lignin can be utilized and extracted for producing the degradable plastics, the comprehensive utilization of the wood can be improved, and the environmental pollution can be reduced.
Patent CN109943039A discloses a methylated lignin/PBAT biodegradable plastic and a preparation method thereof, which improves the addition amount of lignin, enables the cost of a final product to be reduced, but has low mechanical properties, and the tensile property, the impact property and the like of a composite material are not obviously improved, thereby limiting the application range of the material.
Disclosure of Invention
The invention provides a biodegradable resin composition and a preparation method thereof, aiming at solving the problem that the mechanical strength loss of the biodegradable resin composition is large in the prior art.
The technical scheme adopted by the invention is as follows: a method for producing a biodegradable resin composition, characterized by comprising: the production raw material formula comprises the following components in percentage by mass: 100 parts of a butanediol adipate-butanediol terephthalate copolymer, 15-30 parts of lignin powder, 5-15 parts of a methyl acrylate copolymer, 0.5-2 parts of an antioxidant, 0.5-7 parts of a chain extender and 0.1-1 part of a nucleating agent.
As a further improvement of the invention, the production raw material formula also comprises 1-5 parts of fluorescent whitening agent. The fluorescent whitening agent can be selected from various fluorescent whitening agents commonly used in the field, for example, one or more of benzoyl peroxide, stilbene derivatives, phenylpyrazoline derivatives, benzimidazole derivatives, phenylpyrazole derivatives, coumarin derivatives and naphthalimide derivatives can be selected.
As a further improvement of the invention, the methyl acrylate copolymer is selected from one of methyl methacrylate, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer and 2-methyl methacrylate-butyl acrylate copolymer.
As a further improvement of the invention, the antioxidant is one or more selected from 2, 6-di-tert-butyl-p-cresol, octadecyl beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4-hydroxydodecanoic acid anilide, 4, 4-di-tert-octyldiphenylamine and methyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
As a further improvement of the present invention, the chain extender is a styrene-glycidyl acrylate copolymer.
As a further improvement of the invention, the nucleating agent is selected from one or more of talcum powder, silicon dioxide, pimelic acid metal soap, aryl carboxylic acid diamide and derivatives thereof, and organic phosphate.
The invention can be implemented according to the following steps:
s1, weighing the raw materials according to the formula of the production raw materials;
s2, drying a butanediol adipate-butanediol terephthalate copolymer and a methyl acrylate copolymer at the temperature of 80-90 ℃ for 4-6 hours, drying lignin powder at the temperature of 100-110 ℃ for 8-10 hours, adding the dried butanediol adipate-butanediol terephthalate copolymer, the lignin powder, the methyl acrylate copolymer, a fluorescent whitening agent, an antioxidant, a chain extender and a nucleating agent into a high-speed mixer at the rotating speed of 500-1000 r/min, and mixing for 4-8 min;
and S3, granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 180-200 ℃, cooling by a water tank, cutting into particles with the diameter of 2-3 mm by a granulator, and drying at 80-90 ℃ for 4-6 h to obtain the biodegradable resin composition granules.
The lignin powder is preferably methylated lignin powder, and can be prepared by the following method: dissolving lignin powder in a sodium hydroxide aqueous solution, adding 1, 4-dioxane into the solution, then placing the solution into a reaction kettle, cooling the mixture to room temperature after the reaction is finished, separating out lignin by using a hydrochloric acid solution, washing the lignin by using deionized water to be neutral, drying and carrying out ball milling to obtain the lignin.
The invention also discloses a biodegradable resin composition, which is prepared by the preparation method of the biodegradable resin composition.
The invention also discloses a degradable plastic product which is characterized in that the production raw materials comprise the biodegradable resin composition. The degradable plastic product can be various plastic products known at present, in particular various degradable plastic films, such as agricultural mulching films, garbage bags or vegetable greenhouse films and the like.
The invention has the beneficial effects that: the biodegradable resin composition and the product have excellent mechanical property and transparency, simultaneously recover and utilize lignin, and have excellent biodegradation performance.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4-hydroxydodecanoic acid acyl aniline, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is aryl carboxylic acid diamide, the fluorescent whitening agent is a phenyl pyrazoline derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is methyl methacrylate.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and methyl methacrylate at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the methyl methacrylate into a high-speed mixer with the rotating speed of 1000r/min, and mixing for 4 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder temperature of 185 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 5 hours at 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example two:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4-hydroxydodecanoic acid acyl aniline, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is aryl carboxylic acid diamide, the fluorescent whitening agent is a phenyl pyrazoline derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is an ethylene-methyl methacrylate copolymer.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and the ethylene-methyl methacrylate copolymer at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the ethylene-methyl methacrylate copolymer, the fluorescent whitening agent, the antioxidant, the chain extender and the nucleating agent into a high-speed mixer with the rotating speed of 500r/min, and mixing for 8 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder temperature of 185 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 6 hours at 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example three:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4-hydroxydodecanoic acid acyl aniline, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is aryl carboxylic acid diamide, the fluorescent whitening agent is a phenyl pyrazoline derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is an ethylene-methyl acrylate copolymer.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and the ethylene-methyl acrylate copolymer at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the ethylene-methyl acrylate copolymer, the fluorescent whitening agent, the antioxidant, the chain extender and the nucleating agent into a high-speed mixer with the rotating speed of 1000r/min, and mixing for 4 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 190 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 5 hours at the temperature of 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example four:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4-hydroxydodecanoic acid acyl aniline, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is aryl carboxylic acid diamide, the fluorescent whitening agent is a phenyl pyrazoline derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is a 2-methyl methacrylate-butyl acrylate copolymer.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and the 2-methyl methacrylate-butyl acrylate copolymer at the temperature of 80 ℃ for 6 hours, drying the methylated lignin powder at the temperature of 105 ℃ for 8.5 hours, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the 2-methyl methacrylate-butyl acrylate copolymer, the fluorescent whitening agent, the antioxidant, the chain extender and the nucleating agent into a high-speed mixer at the rotating speed of 1000r/min, and mixing for 4 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 190 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 5 hours at the temperature of 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example five:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4, 4-di-tert-octyldiphenylamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is organic phosphate, the fluorescent brightener is a naphthalimide derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is an ethylene-methyl methacrylate copolymer.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and the ethylene-methyl methacrylate copolymer at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the ethylene-methyl methacrylate copolymer, the fluorescent whitening agent, the antioxidant, the chain extender and the nucleating agent into a high-speed mixer at the rotating speed of 800r/min, and mixing for 5 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 180 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 4 hours at the temperature of 85 ℃ to obtain the resin composition granular material.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example six:
the resin composition was prepared as follows:
(1) production raw materials are measured according to a production raw material formula shown in table 1, wherein the antioxidant is 4-hydroxydodecanoic acid acyl aniline, the chain extender is a styrene-glycidyl acrylate copolymer, the nucleating agent is organic phosphate, the fluorescent whitening agent is a phenyl pyrazoline derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is methyl methacrylate.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and methyl methacrylate at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the methyl methacrylate into a high-speed mixer with the rotating speed of 900r/min, and mixing for 6 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 180 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 6 hours at the temperature of 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Example seven:
the resin composition was prepared as follows:
(1) the production raw materials are measured according to the formula of the production raw materials shown in table 1, wherein the antioxidant is 2, 6-di-tert-butyl-p-cresol, the chain extender is styrene-glycidyl acrylate copolymer, the nucleating agent is talcum powder, the fluorescent whitening agent is naphthalimide derivative, the lignin powder is methylated lignin powder, and the methyl acrylate copolymer is ethylene-methyl acrylate copolymer.
(2) Drying the butanediol adipate-butylene terephthalate copolymer and the ethylene-methyl acrylate copolymer at 80 ℃ for 6h, drying the methylated lignin powder at 105 ℃ for 8.5h, adding the dried butanediol adipate-butylene terephthalate copolymer, the methylated lignin powder and the ethylene-methyl acrylate copolymer, the fluorescent whitening agent, the antioxidant, the chain extender and the nucleating agent into a high-speed mixer with the rotating speed of 900r/min, and mixing for 6 min.
(3) And granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 190 ℃, cooling by a water tank, cutting into particles with the diameter of 2mm by a granulator, and drying for 5 hours at the temperature of 85 ℃ to obtain the resin composition granules.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Comparative example one:
this comparative example is a control experiment conducted under the same method and conditions as example one, except that: the formula of the production raw materials does not comprise methylated lignin powder and methyl acrylate copolymer, and the specific formula of the production raw materials is shown in table 1.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Comparative example two:
this comparative example is a control experiment conducted under the same method and conditions as example one, except that: the production raw material formula does not contain methyl acrylate copolymer, and the specific production raw material formula is shown in table 1.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Comparative example three:
this comparative example is a control experiment conducted under the same method and conditions as example one, except that: the formula of the production raw materials does not contain the methylated lignin powder, and the specific formula of the production raw materials is shown in table 1.
The obtained resin composition pellets were subjected to tests of tensile strength, elongation at break, flexural modulus and degradability, and the results are shown in Table 2.
Table 1 raw materials for production formula table (in parts by weight)
TABLE 2 table of the results of the property test of the pellets of the resin composition
| Examples | Tensile Strength (MPa) | Elongation at Break (%) | Flexural modulus (MPa) | Percent of degradability/%) |
| Comparative example 1 | 23.5 | 590 | 102 | 90.3 |
| Comparative example No. two | 15.2 | 450 | 123 | 90.5 |
| Comparative example No. three | 29.5 | 105 | 305 | 79.2 |
| Example one | 20.7 | 450 | 290 | 91.7 |
| Example two | 19.2 | 503 | 262 | 92.3 |
| EXAMPLE III | 18.9 | 487 | 282 | 91.5 |
| Example four | 20.6 | 492 | 252 | 92.1 |
| EXAMPLE five | 21.5 | 512 | 243 | 92.5 |
| EXAMPLE six | 20.6 | 489 | 236 | 91.5 |
| EXAMPLE seven | 18.6 | 568 | 205 | 91.4 |
As can be seen from the formula raw materials of the comparative example I, the comparative example II, the comparative example III and the example I in the tables 1 and 2 and the corresponding detection data, the change of the degradability of the resin composition granules is not obvious after the methylated lignin powder is added on the basis of the raw material of the comparative example I; and the addition of the methyl acrylate copolymer on the basis of the raw material of the comparative example I can obviously reduce the degradability of the material. However, when two raw materials with the same proportion as the comparative example are added simultaneously, the material degradation rate is increased to 91.7%, which shows that the synergistic effect of improving the degradation rate of the resin composition particle materials by using the methylated lignin powder and the methyl acrylate copolymer simultaneously is obvious.
Claims (13)
1. A method for producing a biodegradable resin composition, characterized by comprising: the production raw material formula comprises the following components in percentage by mass: 100 parts of a butanediol adipate-butanediol terephthalate copolymer, 15-30 parts of lignin powder, 5-15 parts of a methyl acrylate copolymer, 0.5-2 parts of an antioxidant, 0.5-7 parts of a chain extender and 0.1-1 part of a nucleating agent.
2. The method for producing a biodegradable resin composition according to claim 1, characterized in that: the production raw material formula also comprises 1-5 parts of a fluorescent whitening agent.
3. The method for producing a biodegradable resin composition according to claim 1, characterized in that: the methyl acrylate copolymer is selected from one of methyl methacrylate, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer and 2-methyl methacrylate-butyl acrylate copolymer.
4. The method for producing a biodegradable resin composition according to claim 2, characterized in that: the fluorescent whitening agent is selected from one or more of benzoyl peroxide, stilbene derivatives, phenylpyrazoline derivatives, benzimidazole derivatives, phenylpyrazole derivatives, coumarin derivatives and naphthalimide derivatives.
5. The method for producing a biodegradable resin composition according to claim 1, characterized in that: the antioxidant is selected from one or more of 2, 6-di-tert-butyl-p-cresol, beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 1,1, 3-tri (2-methyl-4 hydroxy-5 tert-butylphenyl) butane, 4-hydroxydodecanoic acid acyl aniline, 4, 4-di-tert-octyldiphenylamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate.
6. The method for producing a biodegradable resin composition according to claim 1, characterized in that: the chain extender is a styrene-glycidyl acrylate copolymer.
7. The method for producing a biodegradable resin composition according to claim 1, characterized in that: the nucleating agent is selected from one or more of talcum powder, silicon dioxide, pimelic acid metal soap, aryl carboxylic acid diamide and derivatives thereof, and organic phosphate.
8. The method for preparing a biodegradable resin composition according to claim 2, comprising the steps of:
s1, weighing the raw materials according to the formula of the production raw materials;
s2, drying a butanediol adipate-butanediol terephthalate copolymer and a methyl acrylate copolymer at the temperature of 80-90 ℃ for 4-6 hours, drying lignin powder at the temperature of 100-110 ℃ for 8-10 hours, adding the dried butanediol adipate-butanediol terephthalate copolymer, the lignin powder, the methyl acrylate copolymer, a fluorescent whitening agent, an antioxidant, a chain extender and a nucleating agent into a high-speed mixer at the rotating speed of 500-1000 r/min, and mixing for 4-8 min;
and S3, granulating the mixed material by a double-screw extruder with a cylinder at the temperature of 180-200 ℃, cooling by a water tank, cutting into particles with the diameter of 2-3 mm by a granulator, and drying at 80-90 ℃ for 4-6 h to obtain the biodegradable resin composition granules.
9. The method for producing a biodegradable resin composition according to any one of claims 1 to 8, characterized in that: the lignin powder is methylated lignin powder.
10. The method of claim 9, wherein the methylated lignin powder is prepared by: dissolving lignin powder in a sodium hydroxide aqueous solution, adding 1, 4-dioxane into the solution, then placing the solution into a reaction kettle, cooling the mixture to room temperature after the reaction is finished, separating out lignin by using a hydrochloric acid solution, washing the lignin by using deionized water to be neutral, drying and carrying out ball milling to obtain the lignin.
11. The biodegradable resin composition obtained by the method for producing a biodegradable resin composition according to any one of claims 1 to 10.
12. A degradable plastic article characterized by: the production raw material comprises the biodegradable resin composition according to claim 11.
13. The degradable plastic article of claim 12, wherein: the degradable plastic product is an agricultural mulching film, a garbage bag or a vegetable greenhouse film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115246988A (en) * | 2022-05-31 | 2022-10-28 | 中琦(泉州)新材料科技有限公司 | Full-biodegradable zinc ion antibacterial and antiviral master batch |
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| CN112552654A (en) * | 2020-11-17 | 2021-03-26 | 中广核俊尔(浙江)新材料有限公司 | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof |
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| CN106832801A (en) * | 2016-12-21 | 2017-06-13 | 济宁明升新材料有限公司 | A kind of lignin modification PBAT biodegradable plastics and preparation method thereof |
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