WO2023045888A1 - Carbon dioxide copolymer composition and preparation method therefor - Google Patents

Carbon dioxide copolymer composition and preparation method therefor Download PDF

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Publication number
WO2023045888A1
WO2023045888A1 PCT/CN2022/119739 CN2022119739W WO2023045888A1 WO 2023045888 A1 WO2023045888 A1 WO 2023045888A1 CN 2022119739 W CN2022119739 W CN 2022119739W WO 2023045888 A1 WO2023045888 A1 WO 2023045888A1
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Prior art keywords
carbon dioxide
composition
dioxide copolymer
copolymer according
parts
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PCT/CN2022/119739
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French (fr)
Chinese (zh)
Inventor
李洪国
王勋林
李宜格
张俊玲
高燊
胡文达
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山东联欣环保科技有限公司
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Publication of WO2023045888A1 publication Critical patent/WO2023045888A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of IPC classification number C08L3/02, in particular to a carbon dioxide copolymer composition and a preparation method thereof.
  • Carbon dioxide copolymer is an ideal fully degradable plastic variety that uses carbon dioxide as a raw material and has excellent biodegradability.
  • degradable materials related to carbon dioxide copolymers have been developed rapidly, which can fundamentally solve the problem of "white pollution” and promote green and sustainable development.
  • factors such as unsatisfactory thermal and mechanical properties of degradable materials prepared by carbon dioxide copolymers limit their promotion and application.
  • Patent CN202011020665.0 provides a functional degradable material with a controllable degradation cycle and its preparation method, through polybutylene terephthalate, carbon dioxide-based copolymer, polybutylene succinate and additives, etc. The interaction between them can prepare fully biodegradable materials with different degradation cycles, which can be applied to different degradation cycles. However, its application is limited due to its poor light stabilizer properties.
  • Patent CN201811563967.5 provides a stretch-resistant degradable barrier plastic packaging film and its preparation method. It uses carbon dioxide copolymer and maleic anhydride as raw materials, and adds monodisperse silica microspheres and other substances, which not only improves the mechanical properties , and improve the thermal stability of the middle barrier layer. However, its preparation is complicated and its production cost is relatively high, which cannot fully meet the needs of customers.
  • the object of the present invention is to solve the above-mentioned technical problems.
  • the first aspect of the present invention provides a carbon dioxide copolymer composition, including the following raw materials: PPCP, filler; the mass ratio of the PPCP to the filler is 100:(1-500).
  • the raw materials also include epoxy compounds, phosphate ester compounds, plasticizers, acid anhydride compounds, coupling agents, lubricants, anti-aging systems, pigments, citric acid, and at least one of benzoyl peroxide A sort of.
  • the raw materials include 100 parts of PPCP, 1-500 parts of fillers, 2-5 parts of epoxy compounds, 0.5-1.5 parts of phosphate compounds, 3-5 parts of plasticizers, and 1.5 parts of acid anhydride compounds. -2.5 parts, 1-2 parts of coupling agent, 0.2-0.5 parts of lubricant, 0.3-0.7 parts of anti-aging system, 1-3 parts of pigment, 0.7-1.5 parts of citric acid, 0.1-0.2 parts of benzoyl peroxide.
  • the filler includes inorganic filler and/or organic filler.
  • the inorganic filler includes calcium carbonate, talcum powder, clay, white carbon black, barium sulfate, aluminum hydroxide, magnesium hydroxide, asbestos, glass microspheres, glass fiber, red mud, fly ash, carbon black at least one.
  • the organic filler includes at least one of starch, wood flour and plant straw.
  • the mass ratio of the PPCP to the filler is 100:(50-300).
  • the mass ratio of the PPCP to the filler is 100:(80-120).
  • the epoxy compound includes a first epoxy compound and a second epoxy compound.
  • the weight ratio of the first epoxy compound to the second epoxy compound is (8-12):(1-3).
  • the epoxy value of the first epoxy compound is 6.5-7.5.
  • the average molecular weight of the first epoxy compound is 800-1200.
  • the iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g.
  • the epoxy equivalent weight of the second epoxy compound is 270-350.
  • the average molecular weight of the second epoxy compound is 7000-7500.
  • the carbon dioxide copolymer composition prepared has excellent biodegradability and mechanical properties.
  • its processing window is narrow, and it is prone to defects such as thermal degradation, which severely limits its application range.
  • the present invention finds that the addition of epoxy compounds with different epoxy values can significantly improve its processing performance, improve its mechanical properties and thermal stability.
  • the epoxy group contained in the epoxy compound can react with the active group contained in PPCP and other substances, so that the dispersed phase becomes blurred, the force between the two phase interfaces is improved, and the melting of the composition of the carbon dioxide copolymer is improved. Bulk viscosity, so that the composition of the carbon dioxide copolymer has better processability, thereby improving the mechanical properties and thermal degradation of the carbon dioxide copolymer.
  • the weight ratio of the epoxy compound to the plasticizer is (3-4):(3-4).
  • the phosphoric acid ester compound includes at least one of triphenyl phosphite, trialkyl phosphate, toluene xylyl phosphate, and diphenyl-octyl phosphate.
  • the phosphoric acid ester compound includes triphenyl phosphite and diphenyl-octyl phosphate.
  • the weight ratio of the triphenyl phosphite to diphenyl-octyl phosphate is (5-8): (1-3).
  • the weight ratio of the plasticizer to the phosphate compound is (3-4):(0.7-1.2).
  • the acid anhydride compound includes at least one of maleic anhydride, succinic anhydride, succinic anhydride, phthalic anhydride and trimellitic anhydride.
  • the plasticizer includes at least one of glycerin, polyethylene glycol, polypropylene glycol, citric acid ester, sorbitol ester and polycaprolactone.
  • the plasticizer includes glycerin, citrate, polycaprolactone.
  • the weight ratio of glycerin, citric acid ester and polycaprolactone is (5-8):(1-2):(2-3).
  • the present invention discovers that glycerin, citrate, polycaprolactone can significantly improve the degradability and mechanical properties of the composition of carbon dioxide copolymer, presumably because the plasticizer is inserted into the molecular chain of the composition of carbon dioxide copolymer
  • glycerin, citrate, polycaprolactone containing polar groups will interact with reactive groups contained in the composition of carbon dioxide copolymer, especially when the glycerin, citrate, polycaprolactone
  • the weight ratio is (5-8): (1-2): (2-3)
  • it can effectively improve the interaction force between the molecular chains of the carbon dioxide copolymer composition and the arrangement density of the molecular chains between the unit cells, Enhances the plasticizing effect and water resistance of the system.
  • the average molecular weight of the polycaprolactone is 45000-55000.
  • the citric acid ester comprises triethyl citrate, tributyl citrate, trioctyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, acetyl lemon At least one kind of tri-n-hexyl ester.
  • the coupling agent includes at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent and rare earth coupling agent.
  • the coupling agent is a silane coupling agent.
  • the silane coupling agent includes ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidyl etheroxypropyltrimethoxysilane, ethylene At least one of vinyltriethoxysilane and vinyltris( ⁇ -methoxyethoxy)silane.
  • the silane coupling agent includes ⁇ -aminopropyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane.
  • the weight ratio of the ⁇ -aminopropyltriethoxysilane to ⁇ -methacryloxypropyltrimethoxysilane is (1-3):(5-8).
  • the lubricant includes stearic acid, calcium stearate and polyethylene wax.
  • the weight ratio of the stearic acid, calcium stearate and polyethylene wax is 1:(1-2):(3-5).
  • the polyethylene wax has an average molecular weight of 1600-2200.
  • the antioxidant system includes light stabilizers and antioxidants.
  • the weight ratio of the light stabilizer to the antioxidant is (3-5):(1-3).
  • the light stabilizer is a hindered amine light stabilizer.
  • the average molecular weight of the light stabilizer is 3000-4000.
  • the hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol.
  • the antioxidant includes antioxidant 1010, antioxidant 168, and thiosulfate DLTDP.
  • the weight ratio of the antioxidant 1010, antioxidant 168, and thiosulfate DLTDP is (8-12):(13-17):(5-10).
  • the pigment includes at least one of channel black, titanium dioxide, cadmium yellow, phthalocyanine blue, ultramarine blue, iron oxide red, azo red, and azo yellow.
  • the pigment is titanium dioxide.
  • the rutile content in the titanium dioxide is ⁇ 98%.
  • the weight ratio of the acid anhydride compound to citric acid is (1.8-2.3): (0.8-1.2).
  • the second aspect of the present invention provides a method for preparing a carbon dioxide copolymer composition, comprising the following steps: 1) pre-mixing PPCP and filler; 2) adding the mixture into a melting and kneading device for preparation.
  • the preparation method includes the following steps: pre-dry PPCP and filler at 60°C for 4 hours, then mix in a mixer for 3 minutes, then add the remaining raw materials and continue mixing for 2 minutes, and finally add the premixed mixture to the twin-screw extruder In the extruder, extrude and granulate at 100°C-180°C to obtain a carbon dioxide copolymer composition.
  • the present invention uses PPCP as the matrix and various fillers as the carbon dioxide copolymer composition prepared as the reinforcing filling material, through the addition of epoxy compounds with different epoxy values and the use of glycerin, citric acid ester, polycaprolactone compound additive
  • the plastic system improves the intermolecular interaction of the carbon dioxide copolymer composition, so that it has good mechanical properties and hydrophobicity, and at the same time assists a specific anti-aging system to scavenge free radicals, inhibiting the degradation and aging of the carbon dioxide copolymer composition Chain reaction, further improving its light stability and thermal stability, prolonging the life cycle of biodegradable plastics.
  • the prepared carbon dioxide copolymer composition has wide versatility and can be used to prepare sheets and pipes, film products, injection molded parts, foamed products, and various cushioning packaging and insulation materials.
  • a carbon dioxide copolymer composition comprising the following raw materials: 100 parts of PPCP, 100 parts of filler, 3.2 parts of epoxy compounds, 1.2 parts of phosphoric acid ester compounds, 2 parts of acid anhydride compounds, 3.2 parts of plasticizer, coupling agent 1.2 parts, lubricant 0.4 parts, anti-aging system 0.6 parts, pigment 1.5 parts, citric acid 1 part, benzoyl peroxide 0.12 parts.
  • the PPCP was purchased from Shandong Lianxin Environmental Protection Technology Co., Ltd.
  • Described filler is calcium carbonate, and described calcium carbonate is heavy calcium carbonate, and described calcium carbonate carries out surface treatment with 1% titanate coupling agent.
  • the average particle diameter of the filler is 23um.
  • the filler was purchased from Guilin Sanxin New Materials Co., Ltd.
  • the epoxy compound includes a first epoxy compound and a second epoxy compound.
  • the weight ratio of the first epoxy compound package to the second epoxy compound is 10:2.
  • the epoxy value of the first epoxy compound is 6.83.
  • the average molecular weight of the first epoxy compound is 1000.
  • the iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g.
  • the first epoxy compound is epoxy soybean oil, available from Termoplasticos DelSur S.A, model: GreenSoft D epoxy soybean oil.
  • the epoxy equivalent weight of the second epoxy compound is 310.
  • the average molecular weight of the second epoxy compound is 7250.
  • the second epoxy compound was purchased from Shanghai Haibing New Material Technology Co., Ltd., model: ADR-4468.
  • the phosphate ester compounds include triphenyl phosphite and diphenyl-octyl phosphate.
  • the weight ratio of the triphenyl phosphite to diphenyl-octyl phosphate is 7:2.
  • the acid anhydride compound is maleic anhydride.
  • the plasticizer includes glycerin, citrate, polycaprolactone.
  • the weight ratio of glycerin, citrate and polycaprolactone is 7:2:3.
  • the citric acid ester is acetyl tributyl citrate, and the average molecular weight of the polycaprolactone is 50,000. Purchased from Hunan Juren Chemical New Material Technology Co., Ltd., model: PCL-6500.
  • the coupling agent is a silane coupling agent.
  • the silane coupling agent includes ⁇ -aminopropyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane.
  • the weight ratio of ⁇ -aminopropyltriethoxysilane to ⁇ -methacryloxypropyltrimethoxysilane is 2:6.
  • the lubricants include stearic acid, calcium stearate and polyethylene wax.
  • the weight ratio of the stearic acid, calcium stearate and polyethylene wax is 1:1.5:3.5.
  • the average particle diameter of described calcium stearate is 75um.
  • the average molecular weight of the polyethylene wax is 1900.
  • the lubricants were purchased from Shandong Baolilai Plastic Additives Co., Ltd.
  • the antioxidant system includes light stabilizers and antioxidants.
  • the weight ratio of the light stabilizer and antioxidant is 4:2.
  • the light stabilizer is a hindered amine light stabilizer.
  • the average molecular weight of the light stabilizer is 3550.
  • the hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol (CAS number: 65447-77-0).
  • the light stabilizer was purchased from Yixing Angel Synthetic Chemical Co., Ltd., model: hindered amine light stabilizer 622.
  • the antioxidants include antioxidant 1010, antioxidant 168, and thiosulfate DLTDP.
  • the weight ratio of the antioxidant 1010, antioxidant 168, and thiosulfate DLTDP is 10:15:8.
  • the pigment is titanium dioxide.
  • the rutile content in the titanium dioxide is 99%.
  • the pigments were purchased from Dongguan Jishun Import and Export Co., Ltd.
  • a method for preparing a carbon dioxide copolymer composition comprising the steps of: pre-drying PPCP and filler at 60°C for 4 hours, then mixing in a mixer for 3 minutes, then adding the remaining raw materials and continuing mixing for 2 minutes, and finally mixing the premix Put it into a twin-screw extruder, extrude and granulate at 150° C. to obtain a carbon dioxide copolymer composition.
  • a carbon dioxide copolymer composition the specific implementation is the same as in Example 1, except that the filler is 60 parts, and the filler is talcum powder.
  • the talc powder is surface treated with 1% silane coupling agent.
  • the average particle size of the talcum powder is 23um.
  • the filler was purchased from Penglai Yongfengda Superfine Talc Powder Factory.
  • a carbon dioxide copolymer composition the specific implementation is the same as in Example 1, except that the filler is 50 parts, and the filler is modified starch.
  • the modified starch used is obtained by extruding and granulating cornstarch: glycerol at a weight ratio of 10:3.
  • the modified starch was purchased from Dezhou Runde Starch Co., Ltd.
  • a carbon dioxide copolymer composition the specific implementation is the same as in Example 1, except that the filler is 50 parts, and the filler is wood flour.
  • the wood flour is pine flour, and the average particle size of the wood flour is 180um.
  • the wood flour was purchased from Jianshi Mineral Powder Factory in Lingshou County.
  • a carbon dioxide copolymer composition the specific embodiment is the same as that of Example 1, except that the weight ratio of the first epoxy compound to the second epoxy compound is 7:2.
  • a carbon dioxide copolymer composition the specific embodiment is the same as that of Example 1, except that the weight ratio of glycerin, citrate, and polycaprolactone is 7:2:1.
  • composition of the obtained carbon dioxide copolymer into a single-screw extruder, control the temperature at 195° C., and the rotation speed at 70 r/min to obtain a sheet, and perform the following tests:
  • Biodegradability test Test according to the national standard GB/T19277, the temperature is 58 ⁇ 2°C, and the composting time is 3 months.

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  • 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

A carbon dioxide copolymer composition and a preparation method therefor. The following raw materials are comprised: PPCP and a filler; the mass ratio of the PPCP to the filler is 100:(1-500). The carbon dioxide copolymer composition provided by the present invention and the carbon dioxide copolymer composition prepared by means of the preparation method have not only excellent mechanical properties and degradability but also good hydrophobicity.

Description

一种二氧化碳共聚物的组合物及其制备方法Composition of a kind of carbon dioxide copolymer and preparation method thereof
本申请要求于2021年09月24日提交中国专利局、申请号为202111118663.X、发明名称为“一种二氧化碳共聚物的组合物及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on September 24, 2021, the application number is 202111118663.X, and the invention title is "a carbon dioxide copolymer composition and its preparation method", the entire content of which Incorporated in this application by reference.
技术领域technical field
本发明涉及IPC分类号C08L3/02技术领域，具体涉及一种二氧化碳共聚物的组合物及其制备方法。The invention relates to the technical field of IPC classification number C08L3/02, in particular to a carbon dioxide copolymer composition and a preparation method thereof.
背景技术Background technique
二氧化碳共聚物是利用二氧化碳为原料，具有优异的生物降解性能的一种理想的全降解型塑料品种。近年来，随着科学技术的发展，与二氧化碳共聚物有关的可降解性材料得到迅速发展，可以从根本上解决“白色污染”问题，促进绿色可持续发展。但采用二氧化碳共聚物制备的可降解材料的热学和力学性能不理想等因素限制了其推广和应用。Carbon dioxide copolymer is an ideal fully degradable plastic variety that uses carbon dioxide as a raw material and has excellent biodegradability. In recent years, with the development of science and technology, degradable materials related to carbon dioxide copolymers have been developed rapidly, which can fundamentally solve the problem of "white pollution" and promote green and sustainable development. However, factors such as unsatisfactory thermal and mechanical properties of degradable materials prepared by carbon dioxide copolymers limit their promotion and application.
专利CN202011020665.0提供了一种可控降解周期的功能性可降解材料及其制备方法，通过聚对苯二甲酸丁二酯、二氧化碳基共聚物、聚丁二酸丁二醇酯及助剂等之间相互作用，制备得到不同降解周期的全生物降解材料，可以适用于不同降解周期。但由于光稳定剂性较差，限制了其应用。Patent CN202011020665.0 provides a functional degradable material with a controllable degradation cycle and its preparation method, through polybutylene terephthalate, carbon dioxide-based copolymer, polybutylene succinate and additives, etc. The interaction between them can prepare fully biodegradable materials with different degradation cycles, which can be applied to different degradation cycles. However, its application is limited due to its poor light stabilizer properties.
专利CN201811563967.5提供了一种耐拉伸的可降解阻隔塑料包装膜及制备方法，以二氧化碳共聚物和马来酸酐为原料，辅助加入单分散二氧化硅微球等物质，不仅提升了力学性能，而且改善中间阻隔层的热稳定性。但其制备复杂，生产成本较高，无法充分满足客户需要。Patent CN201811563967.5 provides a stretch-resistant degradable barrier plastic packaging film and its preparation method. It uses carbon dioxide copolymer and maleic anhydride as raw materials, and adds monodisperse silica microspheres and other substances, which not only improves the mechanical properties , and improve the thermal stability of the middle barrier layer. However, its preparation is complicated and its production cost is relatively high, which cannot fully meet the needs of customers.
发明内容Contents of the invention
本发明的目的在于解决上述技术问题。The object of the present invention is to solve the above-mentioned technical problems.
本发明的第一个方面提供了一种二氧化碳共聚物的组合物，包括以下原料：PPCP，填料；所述PPCP和填料的质量比为100:(1-500)。The first aspect of the present invention provides a carbon dioxide copolymer composition, including the following raw materials: PPCP, filler; the mass ratio of the PPCP to the filler is 100:(1-500).
优选的，所述原料还包括环氧类化合物，磷酸酯类化合物，增塑剂，酸酐类化合物，偶联剂，润滑剂，防老化体系，颜料，柠檬酸，过氧化苯 甲酰中的至少一种。Preferably, the raw materials also include epoxy compounds, phosphate ester compounds, plasticizers, acid anhydride compounds, coupling agents, lubricants, anti-aging systems, pigments, citric acid, and at least one of benzoyl peroxide A sort of.
优选的，按重量份计，原料包括PPCP 100份，填料1-500份，环氧类化合物2-5份，磷酸酯类化合物0.5-1.5份，增塑剂3-5份，酸酐类化合物1.5-2.5份，偶联剂1-2份，润滑剂0.2-0.5份，防老化体系0.3-0.7份，颜料1-3份，柠檬酸0.7-1.5份，过氧化苯甲酰0.1-0.2份。Preferably, in parts by weight, the raw materials include 100 parts of PPCP, 1-500 parts of fillers, 2-5 parts of epoxy compounds, 0.5-1.5 parts of phosphate compounds, 3-5 parts of plasticizers, and 1.5 parts of acid anhydride compounds. -2.5 parts, 1-2 parts of coupling agent, 0.2-0.5 parts of lubricant, 0.3-0.7 parts of anti-aging system, 1-3 parts of pigment, 0.7-1.5 parts of citric acid, 0.1-0.2 parts of benzoyl peroxide.
填料filler
优选的，所述填料包括无机填料和/或有机填料。Preferably, the filler includes inorganic filler and/or organic filler.
优选的，所述无机填料包括碳酸钙，滑石粉，陶土，白炭黑，硫酸钡，氢氧化铝，氢氧化镁，石棉，玻璃微珠，玻璃纤维，赤泥，粉煤灰，碳黑的至少一种。Preferably, the inorganic filler includes calcium carbonate, talcum powder, clay, white carbon black, barium sulfate, aluminum hydroxide, magnesium hydroxide, asbestos, glass microspheres, glass fiber, red mud, fly ash, carbon black at least one.
优选的，所述有机填料包括淀粉，木粉，植物秸秆的至少一种。Preferably, the organic filler includes at least one of starch, wood flour and plant straw.
进一步优选的，所述PPCP和填料的质量比为100:(50-300)。Further preferably, the mass ratio of the PPCP to the filler is 100:(50-300).
更进一步优选的，所述PPCP和填料的质量比为100:(80-120)。More preferably, the mass ratio of the PPCP to the filler is 100:(80-120).
环氧类化合物epoxy compound
优选的，所述环氧类化合物包括第一环氧类化合物包和第二环氧类化合物。所述第一环氧类化合物和第二环氧类化合物的重量比为(8-12)：(1-3)。Preferably, the epoxy compound includes a first epoxy compound and a second epoxy compound. The weight ratio of the first epoxy compound to the second epoxy compound is (8-12):(1-3).
优选的，所述第一环氧类化合物的环氧值为6.5-7.5。Preferably, the epoxy value of the first epoxy compound is 6.5-7.5.
优选的，所述第一环氧类化合物的平均分子量为800-1200。Preferably, the average molecular weight of the first epoxy compound is 800-1200.
优选的，所述第一环氧类化合物的碘值为0.67/100g，酸值为0.7KOH/g。Preferably, the iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g.
优选的，所述第二环氧类化合物的环氧当量为270-350。Preferably, the epoxy equivalent weight of the second epoxy compound is 270-350.
优选的，所述第二环氧类化合物的平均分子量为7000-7500。Preferably, the average molecular weight of the second epoxy compound is 7000-7500.
以PPCP为基体，以各种填料为增强填充物质，制备得到的二氧化碳共聚物的组合物具有优异的生物降解性和力学性能。但受限于材料本身的性质，导致其加工窗口窄，容易发生热降解等缺陷，严重限制了其应用范围。本发明意外研究发现通过不同环氧值的环氧化合物的加入可以明显改善其加工性能，提高其力学性能和热稳定性。推测是由于环氧化合物含有的环氧基团可以与PPCP等物质含有的活性基团发生反应，使分散相变得模糊，改善两相界面间的作用力，提高二氧化碳共聚物的组合物的熔体粘 度，从而使二氧化碳共聚物的组合物具有更好的加工性能，进而提高了二氧化碳共聚物的力学性能和热降解性。Using PPCP as a matrix and various fillers as reinforcing fillers, the carbon dioxide copolymer composition prepared has excellent biodegradability and mechanical properties. However, limited by the nature of the material itself, its processing window is narrow, and it is prone to defects such as thermal degradation, which severely limits its application range. Surprisingly, the present invention finds that the addition of epoxy compounds with different epoxy values can significantly improve its processing performance, improve its mechanical properties and thermal stability. It is speculated that the epoxy group contained in the epoxy compound can react with the active group contained in PPCP and other substances, so that the dispersed phase becomes blurred, the force between the two phase interfaces is improved, and the melting of the composition of the carbon dioxide copolymer is improved. Bulk viscosity, so that the composition of the carbon dioxide copolymer has better processability, thereby improving the mechanical properties and thermal degradation of the carbon dioxide copolymer.
在一种优选的实施方式中，所述环氧类化合物和增塑剂的重量比为(3-4)：(3-4)。In a preferred embodiment, the weight ratio of the epoxy compound to the plasticizer is (3-4):(3-4).
磷酸酯类化合物Phosphate compounds
优选的，所述磷酸酯类化合物包括亚磷酸三苯酯，磷酸三烷基酯，磷酸甲苯二甲苯酯，磷酸二苯一辛酯的至少一种。Preferably, the phosphoric acid ester compound includes at least one of triphenyl phosphite, trialkyl phosphate, toluene xylyl phosphate, and diphenyl-octyl phosphate.
进一步优选的，所述磷酸酯类化合物包括亚磷酸三苯酯和磷酸二苯一辛酯。所述亚磷酸三苯酯和磷酸二苯一辛酯的重量比为(5-8)：(1-3)。Further preferably, the phosphoric acid ester compound includes triphenyl phosphite and diphenyl-octyl phosphate. The weight ratio of the triphenyl phosphite to diphenyl-octyl phosphate is (5-8): (1-3).
在一种优选的实施方式中，所述增塑剂和磷酸酯类化合物的重量比为(3-4)：(0.7-1.2)。In a preferred embodiment, the weight ratio of the plasticizer to the phosphate compound is (3-4):(0.7-1.2).
酸酐类化合物Anhydrides
优选的，所述酸酐类化合物包括顺丁烯二酸酐，琥珀酸酐，丁二酸酐，邻苯二甲酸酐，偏苯三酸酐的至少一种。Preferably, the acid anhydride compound includes at least one of maleic anhydride, succinic anhydride, succinic anhydride, phthalic anhydride and trimellitic anhydride.
增塑剂plasticizer
优选的，所述增塑剂包括甘油，聚乙二醇，聚丙二醇，柠檬酸酯，山梨醇酯，聚己内酯的至少一种。Preferably, the plasticizer includes at least one of glycerin, polyethylene glycol, polypropylene glycol, citric acid ester, sorbitol ester and polycaprolactone.
进一步优选的，所述增塑剂包括甘油，柠檬酸酯，聚己内酯。所述甘油，柠檬酸酯，聚己内酯的重量比为(5-8)：(1-2)：(2-3)。Further preferably, the plasticizer includes glycerin, citrate, polycaprolactone. The weight ratio of glycerin, citric acid ester and polycaprolactone is (5-8):(1-2):(2-3).
本发明意外研究发现通过甘油，柠檬酸酯，聚己内酯可以显著提高二氧化碳共聚物的组合物的可降解性和力学性能，推测是由于增塑剂插人二氧化碳共聚物的组合物的分子链之间，同时甘油，柠檬酸酯，聚己内酯含有极性基团会与二氧化碳共聚物的组合物含有的活性基团相互作用，尤其是当所述甘油，柠檬酸酯，聚己内酯的重量比为(5-8)：(1-2)：(2-3)时，能有效改善二氧化碳共聚物的组合物分子链间的相互作用力和分子链在晶胞间的排列密度，增强体系的塑化作用和耐水性。The present invention discovers that glycerin, citrate, polycaprolactone can significantly improve the degradability and mechanical properties of the composition of carbon dioxide copolymer, presumably because the plasticizer is inserted into the molecular chain of the composition of carbon dioxide copolymer Between, while glycerin, citrate, polycaprolactone containing polar groups will interact with reactive groups contained in the composition of carbon dioxide copolymer, especially when the glycerin, citrate, polycaprolactone When the weight ratio is (5-8): (1-2): (2-3), it can effectively improve the interaction force between the molecular chains of the carbon dioxide copolymer composition and the arrangement density of the molecular chains between the unit cells, Enhances the plasticizing effect and water resistance of the system.
优选的，所述聚己内酯的平均分子量为45000-55000。Preferably, the average molecular weight of the polycaprolactone is 45000-55000.
优选的，所述柠檬酸酯包括柠檬酸三乙酯，柠檬酸三丁酯，柠檬酸三辛酯，乙酰柠檬酸三乙酯，乙酰柠檬酸三丁酯，乙酰柠檬酸三辛酯，乙酰柠檬酸三正己酯的至少一种。Preferably, the citric acid ester comprises triethyl citrate, tributyl citrate, trioctyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, acetyl lemon At least one kind of tri-n-hexyl ester.
偶联剂coupling agent
优选的，所述偶联剂包括硅烷偶联剂，钛酸酯偶联剂，铝酸酯偶联剂，稀土偶联剂的至少一种。Preferably, the coupling agent includes at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent and rare earth coupling agent.
进一步优选的，所述偶联剂为硅烷偶联剂。Further preferably, the coupling agent is a silane coupling agent.
优选的，所述硅烷偶联剂包括γ-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷，γ-缩水甘油醚氧丙基三甲氧基硅烷，乙烯基三乙氧基硅烷，乙烯基三(β-甲氧乙氧基)硅烷的至少一种。Preferably, the silane coupling agent includes γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, ethylene At least one of vinyltriethoxysilane and vinyltris(β-methoxyethoxy)silane.
进一步优选的，所述硅烷偶联剂包括γ-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷。所述γ-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷的重量比为(1-3)：(5-8)。Further preferably, the silane coupling agent includes γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane. The weight ratio of the γ-aminopropyltriethoxysilane to γ-methacryloxypropyltrimethoxysilane is (1-3):(5-8).
润滑剂lubricant
优选的，所述润滑剂包括硬脂酸，硬脂酸钙和聚乙烯蜡。所述硬脂酸，硬脂酸钙，聚乙烯蜡的重量比为1：(1-2)：(3-5)。Preferably, the lubricant includes stearic acid, calcium stearate and polyethylene wax. The weight ratio of the stearic acid, calcium stearate and polyethylene wax is 1:(1-2):(3-5).
优选的，所述聚乙烯蜡的平均分子量为1600-2200。Preferably, the polyethylene wax has an average molecular weight of 1600-2200.
防老化体系Anti-aging system
优选的，所述抗氧化体系包括光稳定剂和抗氧剂。所述光稳定剂和抗氧剂的重量比为(3-5)：(1-3)。Preferably, the antioxidant system includes light stabilizers and antioxidants. The weight ratio of the light stabilizer to the antioxidant is (3-5):(1-3).
优选的，所述光稳定剂为受阻胺类光稳定剂。Preferably, the light stabilizer is a hindered amine light stabilizer.
优选的，所述光稳定剂的平均分子量为3000-4000。Preferably, the average molecular weight of the light stabilizer is 3000-4000.
优选的，所述受阻胺类光稳定剂为丁二酸与4-羟基-2,2,6,6-四甲-1哌啶醇的聚合体。Preferably, the hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol.
优选的，所述抗氧剂包括抗氧剂1010，抗氧剂168，硫代硫酸酯类DLTDP。所述抗氧剂1010，抗氧剂168，硫代硫酸酯类DLTDP的重量比为(8-12)：(13-17)：(5-10)。Preferably, the antioxidant includes antioxidant 1010, antioxidant 168, and thiosulfate DLTDP. The weight ratio of the antioxidant 1010, antioxidant 168, and thiosulfate DLTDP is (8-12):(13-17):(5-10).
颜料pigment
优选的，所述颜料包括槽法炭黑，钛白粉，镉黄，酞菁蓝，群青，氧化铁红，偶氮红，偶氮黄的至少一种。Preferably, the pigment includes at least one of channel black, titanium dioxide, cadmium yellow, phthalocyanine blue, ultramarine blue, iron oxide red, azo red, and azo yellow.
进一步优选的，所述颜料为钛白粉。Further preferably, the pigment is titanium dioxide.
优选的，所述钛白粉中金红石型含量≥98％。Preferably, the rutile content in the titanium dioxide is ≥98%.
在一种优选的实施方式中，所述酸酐类化合物和柠檬酸的重量比为 (1.8-2.3)：(0.8-1.2)。In a preferred embodiment, the weight ratio of the acid anhydride compound to citric acid is (1.8-2.3): (0.8-1.2).
本发明的第二个方面提供了一种二氧化碳共聚物的组合物的制备方法，包括以下步骤：1)将PPCP和填料预先混合；2)将混合物加入熔融混炼设备中进行制备。The second aspect of the present invention provides a method for preparing a carbon dioxide copolymer composition, comprising the following steps: 1) pre-mixing PPCP and filler; 2) adding the mixture into a melting and kneading device for preparation.
优选的，所述制备方法，包括以下步骤：将PPCP、填料预先在60℃下干燥4小时，然后在混合机中混合3min，然后加入剩余原料继续混合2min，最后将预混物加入双螺杆挤出机中，在100℃-180℃下挤出造粒得到二氧化碳共聚物的组合物。Preferably, the preparation method includes the following steps: pre-dry PPCP and filler at 60°C for 4 hours, then mix in a mixer for 3 minutes, then add the remaining raw materials and continue mixing for 2 minutes, and finally add the premixed mixture to the twin-screw extruder In the extruder, extrude and granulate at 100°C-180°C to obtain a carbon dioxide copolymer composition.
有益效果：Beneficial effect:
目前市面上存在的生物可降解塑料为实现优异的可降解性能，往往会采取牺牲其他性能的方法，导致制备得到的生物可降解塑料力学性能差，容易发生热降解和光降解等，严重影响生物可降解塑料的使用周期，限制了其应用范围。In order to achieve excellent degradable performance, the biodegradable plastics currently on the market often adopt methods of sacrificing other properties, resulting in poor mechanical properties of the prepared biodegradable plastics, prone to thermal degradation and photodegradation, etc., which seriously affect biodegradable plastics. The life cycle of degradable plastics limits its scope of application.
本发明以PPCP为基体，以各种填料为增强填充物质制备得到的二氧化碳共聚物的组合物，通过不同环氧值的环氧化合物的加入以及采用甘油，柠檬酸酯，聚己内酯复合增塑体系，改善了二氧化碳共聚物的组合物分子间的相互作用，使其具有良好的力学性能和疏水性，同时辅助以特定的防老体系清除自由基，抑制了二氧化碳共聚物的组合物降解老化的链反应，进一步提高其光稳定性和热稳定性，延长生物可降解塑料的使用周期。除此之外制备得到二氧化碳共聚物的组合物的通用性广，可以用于制备片材和管材，薄膜制品，注塑件，发泡制品以及各种缓冲包装和保温材料等。The present invention uses PPCP as the matrix and various fillers as the carbon dioxide copolymer composition prepared as the reinforcing filling material, through the addition of epoxy compounds with different epoxy values and the use of glycerin, citric acid ester, polycaprolactone compound additive The plastic system improves the intermolecular interaction of the carbon dioxide copolymer composition, so that it has good mechanical properties and hydrophobicity, and at the same time assists a specific anti-aging system to scavenge free radicals, inhibiting the degradation and aging of the carbon dioxide copolymer composition Chain reaction, further improving its light stability and thermal stability, prolonging the life cycle of biodegradable plastics. In addition, the prepared carbon dioxide copolymer composition has wide versatility and can be used to prepare sheets and pipes, film products, injection molded parts, foamed products, and various cushioning packaging and insulation materials.
具体实施方式Detailed ways
实施例Example
实施例1Example 1
一种二氧化碳共聚物的组合物，包括以下原料：PPCP 100份，填料100份，环氧类化合物3.2份，磷酸酯类化合物1.2份，酸酐类化合物2份，增塑剂3.2份，偶联剂1.2份，润滑剂0.4份，防老化体系0.6份，颜料1.5份，柠檬酸1份，过氧化苯甲酰0.12份。A carbon dioxide copolymer composition, comprising the following raw materials: 100 parts of PPCP, 100 parts of filler, 3.2 parts of epoxy compounds, 1.2 parts of phosphoric acid ester compounds, 2 parts of acid anhydride compounds, 3.2 parts of plasticizer, coupling agent 1.2 parts, lubricant 0.4 parts, anti-aging system 0.6 parts, pigment 1.5 parts, citric acid 1 part, benzoyl peroxide 0.12 parts.
所述PPCP购自山东联欣环保科技有限公司。The PPCP was purchased from Shandong Lianxin Environmental Protection Technology Co., Ltd.
所述填料为碳酸钙，所述碳酸钙为重质碳酸钙，所述碳酸钙用1％钛 酸酯偶联剂进行表面处理。所述填料的平均粒径为23um。所述填料购自桂林市三鑫新型材料有限责任公司。Described filler is calcium carbonate, and described calcium carbonate is heavy calcium carbonate, and described calcium carbonate carries out surface treatment with 1% titanate coupling agent. The average particle diameter of the filler is 23um. The filler was purchased from Guilin Sanxin New Materials Co., Ltd.
所述环氧类化合物包括第一环氧类化合物和第二环氧类化合物。所述第一环氧类化合物包和第二环氧类化合物的重量比为10：2。所述第一环氧类化合物的环氧值为6.83。所述第一环氧类化合物的平均分子量为1000。所述第一环氧类化合物的碘值为0.67/100g，酸值为0.7KOH/g。所述第一环氧类化合物为环氧大豆油，购自Termoplasticos DelSur S.A，型号：GreenSoft D环氧大豆油。所述第二环氧类化合物的环氧当量为310。所述第二环氧类化合物的平均分子量为7250。所述第二环氧类化合物购自上海海冰新材料科技有限公司，型号：ADR-4468。The epoxy compound includes a first epoxy compound and a second epoxy compound. The weight ratio of the first epoxy compound package to the second epoxy compound is 10:2. The epoxy value of the first epoxy compound is 6.83. The average molecular weight of the first epoxy compound is 1000. The iodine value of the first epoxy compound is 0.67/100g, and the acid value is 0.7KOH/g. The first epoxy compound is epoxy soybean oil, available from Termoplasticos DelSur S.A, model: GreenSoft D epoxy soybean oil. The epoxy equivalent weight of the second epoxy compound is 310. The average molecular weight of the second epoxy compound is 7250. The second epoxy compound was purchased from Shanghai Haibing New Material Technology Co., Ltd., model: ADR-4468.
所述磷酸酯类化合物包括亚磷酸三苯酯和磷酸二苯一辛酯。所述亚磷酸三苯酯和磷酸二苯一辛酯的重量比为7：2。The phosphate ester compounds include triphenyl phosphite and diphenyl-octyl phosphate. The weight ratio of the triphenyl phosphite to diphenyl-octyl phosphate is 7:2.
所述酸酐类化合物为顺丁烯二酸酐。The acid anhydride compound is maleic anhydride.
所述增塑剂包括甘油，柠檬酸酯，聚己内酯。所述甘油，柠檬酸酯，聚己内酯的重量比为7：2：3。所述柠檬酸酯为乙酰柠檬酸三丁酯，所述聚己内酯的平均分子量为50000。购自湖南聚仁化工新材料科技有限公司，型号：PCL-6500。The plasticizer includes glycerin, citrate, polycaprolactone. The weight ratio of glycerin, citrate and polycaprolactone is 7:2:3. The citric acid ester is acetyl tributyl citrate, and the average molecular weight of the polycaprolactone is 50,000. Purchased from Hunan Juren Chemical New Material Technology Co., Ltd., model: PCL-6500.
所述偶联剂为硅烷偶联剂。所述硅烷偶联剂包括γ-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷。所述γ-氨丙基三乙氧基硅烷，γ-甲基丙烯酰氧基丙基三甲氧基硅烷的重量比为2：6。The coupling agent is a silane coupling agent. The silane coupling agent includes γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane. The weight ratio of γ-aminopropyltriethoxysilane to γ-methacryloxypropyltrimethoxysilane is 2:6.
所述润滑剂包括硬脂酸，硬脂酸钙和聚乙烯蜡。所述硬脂酸，硬脂酸钙，聚乙烯蜡的重量比为1：1.5：3.5。所述硬脂酸钙的平均粒径为75um。所述聚乙烯蜡的平均分子量为1900。所述润滑剂均购自山东宝利莱塑料助剂有限公司。The lubricants include stearic acid, calcium stearate and polyethylene wax. The weight ratio of the stearic acid, calcium stearate and polyethylene wax is 1:1.5:3.5. The average particle diameter of described calcium stearate is 75um. The average molecular weight of the polyethylene wax is 1900. The lubricants were purchased from Shandong Baolilai Plastic Additives Co., Ltd.
所述抗氧化体系包括光稳定剂和抗氧剂。所述光稳定剂和抗氧剂的重量比为4：2。所述光稳定剂为受阻胺类光稳定剂。所述光稳定剂的平均分子量为3550。所述受阻胺类光稳定剂为丁二酸与4-羟基-2,2,6,6-四甲-1哌啶醇的聚合体(CAS号：65447-77-0)。所述光稳定剂购自宜兴市天使合成化学有限公司，型号：受阻胺类光稳定剂622。所述抗氧剂包括抗氧剂1010，抗氧剂168，硫代硫酸酯类DLTDP。所述抗氧剂1010，抗氧剂168， 硫代硫酸酯类DLTDP的重量比为10：15：8。The antioxidant system includes light stabilizers and antioxidants. The weight ratio of the light stabilizer and antioxidant is 4:2. The light stabilizer is a hindered amine light stabilizer. The average molecular weight of the light stabilizer is 3550. The hindered amine light stabilizer is a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol (CAS number: 65447-77-0). The light stabilizer was purchased from Yixing Angel Synthetic Chemical Co., Ltd., model: hindered amine light stabilizer 622. The antioxidants include antioxidant 1010, antioxidant 168, and thiosulfate DLTDP. The weight ratio of the antioxidant 1010, antioxidant 168, and thiosulfate DLTDP is 10:15:8.
所述颜料为钛白粉。所述钛白粉中金红石型含量为99％。所述颜料购自东莞市吉顺进出口有限公司。The pigment is titanium dioxide. The rutile content in the titanium dioxide is 99%. The pigments were purchased from Dongguan Jishun Import and Export Co., Ltd.
一种二氧化碳共聚物的组合物的制备方法，包括以下步骤：将PPCP、填料预先在60℃下干燥4小时，然后在混合机中混合3min，然后加入剩余原料继续混合2min，最后将预混物加入双螺杆挤出机中，在150℃下挤出造粒得到二氧化碳共聚物的组合物。A method for preparing a carbon dioxide copolymer composition, comprising the steps of: pre-drying PPCP and filler at 60°C for 4 hours, then mixing in a mixer for 3 minutes, then adding the remaining raw materials and continuing mixing for 2 minutes, and finally mixing the premix Put it into a twin-screw extruder, extrude and granulate at 150° C. to obtain a carbon dioxide copolymer composition.
实施例2Example 2
一种二氧化碳共聚物的组合物，具体实施方式同实施例1，不同之处在于所述填料为60份，所述填料为滑石粉。所述滑石粉用1％硅烷偶联剂进行表面处理。所述滑石粉的平均粒径为23um。所述填料购自蓬莱市永丰达超细滑石粉厂。A carbon dioxide copolymer composition, the specific implementation is the same as in Example 1, except that the filler is 60 parts, and the filler is talcum powder. The talc powder is surface treated with 1% silane coupling agent. The average particle size of the talcum powder is 23um. The filler was purchased from Penglai Yongfengda Superfine Talc Powder Factory.
实施例3Example 3
一种二氧化碳共聚物的组合物，具体实施方式同实施例1，不同之处在于所述填料为50份，所述填料为变性淀粉。所用变性淀粉是由玉米淀粉：甘油按重量比10:3挤出造粒而得。所述变性淀粉购自德州润德淀粉有限公司。A carbon dioxide copolymer composition, the specific implementation is the same as in Example 1, except that the filler is 50 parts, and the filler is modified starch. The modified starch used is obtained by extruding and granulating cornstarch: glycerol at a weight ratio of 10:3. The modified starch was purchased from Dezhou Runde Starch Co., Ltd.
实施例4Example 4
一种二氧化碳共聚物的组合物，具体实施方式同实施例1，不同之处在于所述填料为50份，所述填料为木粉。所述木粉为松木粉，所述木粉平均粒径为180um。所述木粉购自灵寿县健石矿物粉体厂。A carbon dioxide copolymer composition, the specific implementation is the same as in Example 1, except that the filler is 50 parts, and the filler is wood flour. The wood flour is pine flour, and the average particle size of the wood flour is 180um. The wood flour was purchased from Jianshi Mineral Powder Factory in Lingshou County.
对比例1Comparative example 1
一种二氧化碳共聚物的组合物，具体实施方式同实施例1，不同之处在于所述第一环氧类化合物和第二环氧类化合物的重量比为7：2。A carbon dioxide copolymer composition, the specific embodiment is the same as that of Example 1, except that the weight ratio of the first epoxy compound to the second epoxy compound is 7:2.
对比例2Comparative example 2
一种二氧化碳共聚物的组合物，具体实施方式同实施例1，不同之处在于所述甘油，柠檬酸酯，聚己内酯的重量比为7：2：1。A carbon dioxide copolymer composition, the specific embodiment is the same as that of Example 1, except that the weight ratio of glycerin, citrate, and polycaprolactone is 7:2:1.
性能测试Performance Testing
将得到的二氧化碳共聚物的组合物放入单螺杆挤出机中，控制温度为195℃，转速为70r/min，制得片材，并进行以下测试：Put the composition of the obtained carbon dioxide copolymer into a single-screw extruder, control the temperature at 195° C., and the rotation speed at 70 r/min to obtain a sheet, and perform the following tests:
1.拉伸性能测试：按国标GB/T1040进行测试。1. Tensile performance test: test according to the national standard GB/T1040.
2.生物降解性测试：按国标GB/T19277进行测试，温度为58±2℃条件，时间为堆肥3个月。2. Biodegradability test: Test according to the national standard GB/T19277, the temperature is 58±2℃, and the composting time is 3 months.
表1性能测试结果Table 1 performance test results
 the 拉伸强度MPaTensile strength MPa 降解率％Degradation rate%
实施例1Example 1 23twenty three 100100
实施例2Example 2 22twenty two 100100
实施例3Example 3 22twenty two 100100
实施例4Example 4 21twenty one 100100
对比例1Comparative example 1 1818 9797
对比例2Comparative example 2 1616 9696
以上所述仅是本发明的优选实施方式，应当指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvements and Retouching should also be regarded as the protection scope of the present invention.

Claims (23)

  1. 一种二氧化碳共聚物的组合物，其特征在于，包括以下原料：PPCP，填料；所述PPCP和填料的质量比为100:(1-500)；A composition of carbon dioxide copolymer, is characterized in that, comprises following raw material: PPCP, filler; The mass ratio of described PPCP and filler is 100:(1-500);
    所述填料包括无机填料和/或有机填料；The fillers include inorganic fillers and/or organic fillers;
    所述无机填料包括碳酸钙，滑石粉，陶土，白炭黑，硫酸钡，氢氧化铝，氢氧化镁，石棉，玻璃微珠，玻璃纤维，赤泥，粉煤灰，碳黑的至少一种；The inorganic filler includes at least one of calcium carbonate, talcum powder, clay, white carbon black, barium sulfate, aluminum hydroxide, magnesium hydroxide, asbestos, glass microspheres, glass fibers, red mud, fly ash, and carbon black ;
    所述有机填料包括淀粉，木粉，植物秸秆的至少一种。The organic filler includes at least one of starch, wood flour and plant straw.
  2. 根据权利要求1所述的二氧化碳共聚物的组合物，其特征在于，所述PPCP和填料的质量比为100:(80-120)。The composition of carbon dioxide copolymer according to claim 1, is characterized in that, the mass ratio of described PPCP and filler is 100:(80-120).
  3. 根据权利要求1所述的二氧化碳共聚物的组合物，其特征在于，所述原料还包括环氧类化合物，磷酸酯类化合物，增塑剂，酸酐类化合物，偶联剂，润滑剂，防老化体系，颜料，柠檬酸，过氧化苯甲酰的至少一种。The composition of carbon dioxide copolymer according to claim 1, is characterized in that, described raw material also comprises epoxy compound, phosphoric acid ester compound, plasticizer, acid anhydride compound, coupling agent, lubricant, anti-aging system, pigment, citric acid, and at least one of benzoyl peroxide.
  4. 根据权利要求3所述的二氧化碳共聚物的组合物，其特征在于，按重量份计，包括以下原料：PPCP 100份，填料1-500份，环氧类化合物2-5份，磷酸酯类化合物0.5-1.5份，增塑剂3-5份，酸酐类化合物1.5-2.5份，偶联剂1-2份，润滑剂0.2-0.5份，防老化体系0.3-0.7份，颜料1-3份，柠檬酸0.7-1.5份，过氧化苯甲酰0.1-0.2份。The composition of carbon dioxide copolymer according to claim 3, is characterized in that, by weight, comprises following raw material: 100 parts of PPCP, 1-500 parts of filler, 2-5 parts of epoxy compound, phosphoric acid ester compound 0.5-1.5 parts, 3-5 parts of plasticizer, 1.5-2.5 parts of acid anhydride compounds, 1-2 parts of coupling agent, 0.2-0.5 parts of lubricant, 0.3-0.7 parts of anti-aging system, 1-3 parts of pigment, 0.7-1.5 parts of citric acid, 0.1-0.2 parts of benzoyl peroxide.
  5. 根据权利要求3或4所述的二氧化碳共聚物的组合物，其特征在于，所述环氧类化合物包括第一环氧类化合物和第二环氧类化合物。The composition of the carbon dioxide copolymer according to claim 3 or 4, wherein the epoxy compound comprises a first epoxy compound and a second epoxy compound.
  6. 根据权利要求5所述的二氧化碳共聚物的组合物，其特征在于，所述第一环氧类化合物的环氧值为6.5-7.5。The composition of carbon dioxide copolymer according to claim 5, characterized in that, the epoxy value of the first epoxy compound is 6.5-7.5.
  7. 根据权利要求5所述的二氧化碳共聚物的组合物，其特征在于，所述第二环氧类化合物的环氧当量为270-350。The composition of carbon dioxide copolymer according to claim 5, wherein the epoxy equivalent of the second epoxy compound is 270-350.
  8. 根据权利要求4～7任一项所述的二氧化碳共聚物的组合物，其特征在于，所述环氧类化合物和增塑剂的重量比为(3-4)：(3-4)。The composition of the carbon dioxide copolymer according to any one of claims 4-7, wherein the weight ratio of the epoxy compound to the plasticizer is (3-4):(3-4).
  9. 根据权利要求4所述的二氧化碳共聚物的组合物，其特征在于，所述磷酸酯类化合物包括亚磷酸三苯酯，磷酸三烷基酯，磷酸甲苯二甲苯酯，磷酸二苯一辛酯的至少一种。The composition of carbon dioxide copolymer according to claim 4, is characterized in that, described phosphoric acid ester compound comprises triphenyl phosphite, trialkyl phosphate, toluene xylyl phosphate, diphenyl-octyl phosphate at least one.
  10. 根据权利要求9所述的二氧化碳共聚物的组合物，其特征在于， 所述磷酸酯类化合物包括亚磷酸三苯酯和磷酸二苯一辛酯；所述亚磷酸三苯酯和磷酸二苯一辛酯的重量比为(5-8)：(1-3)。The composition of carbon dioxide copolymer according to claim 9, is characterized in that, described phosphate compound comprises triphenyl phosphite and diphenyl-octyl phosphate; Described triphenyl phosphite and diphenyl-octyl phosphate The weight ratio of octyl ester is (5-8):(1-3).
  11. 根据权利要求3所述的二氧化碳共聚物的组合物，其特征在于，所述增塑剂包括甘油，聚乙二醇，聚丙二醇，柠檬酸酯，山梨醇酯，聚己内酯的至少一种。The composition of carbon dioxide copolymer according to claim 3, is characterized in that, described plasticizer comprises at least one of glycerin, polyethylene glycol, polypropylene glycol, citric acid ester, sorbitol ester, polycaprolactone .
  12. 根据权利要求10所述的二氧化碳共聚物的组合物，其特征在于，所述增塑剂包括甘油，柠檬酸酯和聚己内酯。The composition of carbon dioxide copolymer according to claim 10, wherein the plasticizer comprises glycerin, citrate and polycaprolactone.
  13. 根据权利要求11所述的二氧化碳共聚物的组合物，其特征在于，所述增塑剂中甘油，柠檬酸酯和聚己内酯的重量比为(5-8)：(1-2)：(2-3)。The composition of carbon dioxide copolymer according to claim 11, is characterized in that, in the plasticizer, glycerin, the weight ratio of citric acid ester and polycaprolactone is (5-8): (1-2): (2-3).
  14. 根据权利要求10～12任一项所述的二氧化碳共聚物的组合物，其特征在于，所述增塑剂和磷酸酯类化合物的重量比为(3-4)：(0.7-1.2)。The carbon dioxide copolymer composition according to any one of claims 10-12, characterized in that the weight ratio of the plasticizer to the phosphoric acid ester compound is (3-4):(0.7-1.2).
  15. 根据权利要求4所述的二氧化碳共聚物的组合物，所述润滑剂包括硬脂酸，硬脂酸钙和聚乙烯蜡。The composition of carbon dioxide copolymer according to claim 4, said lubricant comprises stearic acid, calcium stearate and polyethylene wax.
  16. 根据权利要求14所述的二氧化碳共聚物的组合物，所述润滑剂中硬脂酸，硬脂酸钙和聚乙烯蜡的重量比为1：(1-2)：(3-5)。The composition of carbon dioxide copolymer according to claim 14, in the lubricant, the weight ratio of stearic acid, calcium stearate and polyethylene wax is 1: (1-2): (3-5).
  17. 根据权利要求4所述的二氧化碳共聚物的组合物，其特征在于，所述抗氧化体系包括光稳定剂和抗氧剂；The composition of carbon dioxide copolymer according to claim 4, is characterized in that, described antioxidant system comprises light stabilizer and antioxidant;
  18. 根据权利要求16所述的二氧化碳共聚物的组合物，其特征在于，所述光稳定剂为受阻胺类光稳定剂；所述抗氧剂包括抗氧剂1010，抗氧剂168，硫代硫酸酯类DLTDP。The composition of carbon dioxide copolymer according to claim 16, is characterized in that, described light stabilizer is hindered amine light stabilizer; Described antioxidant comprises antioxidant 1010, antioxidant 168, thiosulfuric acid Esters DLTDP.
  19. 根据权利要求17所述的二氧化碳共聚物的组合物，其特征在于，所述抗氧化体系中光稳定剂和抗氧剂的重量比为(3-5)：(1-3)。The composition of carbon dioxide copolymer according to claim 17, characterized in that, the weight ratio of light stabilizer and antioxidant in the antioxidant system is (3-5):(1-3).
  20. 权利要求1所述的二氧化碳共聚物的组合物的制备方法，其特征在于，包括以下步骤：1)将PPCP和填料预先混合，得到混合物；2)将所述混合物加入熔融混炼设备中进行制备。The preparation method of the composition of carbon dioxide copolymer according to claim 1, is characterized in that, comprises the following steps: 1) PPCP and filler are mixed in advance, obtains mixture; 2) described mixture is added in the melt kneading equipment and prepares .
  21. 根据权利要求19所述的制备方法，其特征在于，所述混合前，还包括将PPCP和填料进行干燥；所述干燥的温度为60℃，时间为4h。The preparation method according to claim 19, further comprising drying the PPCP and the filler before the mixing; the drying temperature is 60° C. and the time is 4 hours.
  22. 根据权利要求19所述的制备方法，其特征在于，当所述原料还包括环氧类化合物，磷酸酯类化合物，增塑剂，酸酐类化合物，偶联剂，润滑剂，防老化体系，颜料，柠檬酸，过氧化苯甲酰的至少一种时，所述混 合后还包括将所述PPCP和填料预先混合后，再加入剩余原料继续混合2min，得到混合物；The preparation method according to claim 19, wherein when the raw materials also include epoxy compounds, phosphate ester compounds, plasticizers, acid anhydride compounds, coupling agents, lubricants, anti-aging systems, pigments , citric acid, and at least one of benzoyl peroxide, the mixing also includes pre-mixing the PPCP and the filler, then adding the remaining raw materials and continuing mixing for 2 minutes to obtain a mixture;
    所述剩余原料包括环氧类化合物，磷酸酯类化合物，增塑剂，酸酐类化合物，偶联剂，润滑剂，防老化体系，颜料，柠檬酸，过氧化苯甲酰的至少一种。The remaining raw materials include at least one of epoxy compounds, phosphate ester compounds, plasticizers, acid anhydride compounds, coupling agents, lubricants, anti-aging systems, pigments, citric acid, and benzoyl peroxide.
  23. 根据权利要求19所述的制备方法，其特征在于，所述熔融混炼设备的挤出造粒温度为100～180℃。The preparation method according to claim 19, characterized in that the extrusion granulation temperature of the melting and mixing equipment is 100-180°C.
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