WO2023104139A1 - Composite polymer material with strong impact resistance and preparation method therefor - Google Patents
Composite polymer material with strong impact resistance and preparation method therefor Download PDFInfo
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- WO2023104139A1 WO2023104139A1 PCT/CN2022/137486 CN2022137486W WO2023104139A1 WO 2023104139 A1 WO2023104139 A1 WO 2023104139A1 CN 2022137486 W CN2022137486 W CN 2022137486W WO 2023104139 A1 WO2023104139 A1 WO 2023104139A1
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- polymer material
- composite polymer
- impact resistance
- compatibilizer
- polycaprolactone
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08L69/005—Polyester-carbonates
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Definitions
- the invention relates to the field of polymer compound compositions, and relates to an IPC classification number C08L (2006.01), in particular to a composite polymer material with strong impact resistance.
- Chinese invention patent CN202010814476.4 discloses a degradable plastic composition, which is produced by blending PLA and PBS.
- PLA is expensive, and it is not easy to popularize and use it in the actual production process.
- Chinese invention patent CN201210511722.4 discloses a fully degradable bamboo-plastic composite material with ultra-high toughness. The toughness between the plastic matrix is increased by introducing natural plant fibers, but the addition of natural plant fibers will lead to poor molding effect of the material. It is not suitable for the production of blown film process, which limits the preparation of some products.
- the invention provides a composite polymer material with strong impact resistance.
- the invention provides a composite polymer material with strong impact resistance.
- the preparation raw materials include, in parts by weight: 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, and Compatible agent 0.05-0.2 parts.
- the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide
- the number average molecular weight of the propylene glycol phthalate-propylene carbonate copolymer is 100000-200000 g/mol.
- the melt flow rate of the polycaprolactone at 160° C. is 5.9-7.9 g/10 min.
- the polycaprolactone has a number average molecular weight of 80000-100000 g/mol, a water content of 0.3-0.4%, and a crystallinity of 43-48%.
- the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is (1-7):(4-9).
- the compatibilizer is selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.
- the reactive chain extension compatibilizer is selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic acid type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and oxazoline One or a combination of several types of compatibilizers.
- the weight ratio of polycaprolactone to the compatibilizer is 1:(1-4):0.05.
- the raw materials for preparation also include additives, in parts by weight of 0.1-1 parts.
- the auxiliary agent is selected from one or a combination of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil.
- the auxiliary agent is a combination of talcum powder, titanium dioxide and castor oil.
- the weight ratio of the talcum powder, titanium dioxide and castor oil is 1:(0.5-1.2):(0.5-0.8).
- the present invention also provides a method for preparing a composite polymer material with strong impact resistance described in the above technical solution, comprising the following steps:
- step 2 (3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.
- the composite macromolecule material with strong impact resistance provided by the present invention, by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7), makes composite Polymer materials have good oxygen and water vapor barrier properties, and also have good biodegradability and excellent environmental performance.
- the invention provides a composite polymer material with strong impact resistance.
- the preparation raw materials include, in parts by weight, 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, 0.05-0.2 parts of compatibilizer.
- the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is preferably 100000- 200000g/mol.
- the applicant found that the molecular weight distribution of the propylene glycol phthalate-propylene carbonate copolymer prepared by adding ethylene oxide is relatively narrow, which is conducive to improving the processing and molding performance of composite polymer materials. Under these conditions, the production cost can also be reduced.
- the melt flow rate of the polycaprolactone at 160° C. is preferably 5.9-7.9 g/10 min.
- the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol
- the water content is preferably 0.3-0.4%
- the crystallinity is preferably 43-48%.
- the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol, the water content is preferably 0.35%, and the crystallinity is preferably 45%.
- the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is preferably (1-7): (4-9), more preferably (3-5): (5-7), most preferably 3:7.
- the compatibilizer is preferably selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.
- the reactive chain extension compatibilizer is preferably selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and One or more combinations of oxazoline compatibilizers, more preferably one or more combinations selected from epoxy-type compatibilizers, isocyanate-type compatibilizers and oxazoline-type compatibilizers .
- the weight ratio of polycaprolactone to the compatibilizer is preferably 1:(1-4):(0.01-0.05).
- the raw materials for preparation preferably include auxiliary agents, and the parts by weight are preferably 0.1-1 parts.
- the auxiliary agent is preferably selected from one or more combinations of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil, More preferred is a combination of talc, titanium dioxide and castor oil.
- the weight ratio of the talc powder, titanium dioxide and castor oil is preferably 1:(0.5-1.2):(0.5-0.8), more preferably 1:1:0.7.
- the synergistic effect of titanium dioxide and castor oil can prevent bacteria in the external environment from reaching food. On the surface, reduce the spoilage of food, the fluidity of titanium dioxide in the composite material is not good, the addition of castor oil can promote the movement of titanium dioxide in the composite material, and further increase the use safety effect.
- the synergistic effect of talc and castor oil can weaken the interfacial resistance between PCL and PPCP, reduce the friction between molecules, improve the compatibility between PCL and PPCP, and further improve the impact resistance.
- a second aspect of the present invention provides a method for preparing a composite polymer material with strong impact resistance, comprising the following steps:
- step 2 (3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.
- the present invention has the following beneficial effects:
- the strong composite macromolecular material of impact resistance of the present invention by adopting crystallinity is the polycaprolactone of 45% and amorphous propylene glycol phthalate-propylene carbonate copolymer synergistic effect, has improved Tensile strength and impact resistance of composite polymer materials.
- the composite polymer material with strong impact resistance of the present invention by adding talcum powder, titanium dioxide, and castor oil additives, improves the molding effect of the composite polymer material, and improves the use safety performance of the material, and is especially suitable for Product packaging for food, medicine.
- the composite polymer material with strong impact resistance of the present invention by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7) , so that the composite polymer material has good oxygen and water vapor barrier properties, and also has good biodegradability and excellent environmental performance.
- a composite polymer material with strong impact resistance the preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.05 parts of compatibilizer, auxiliary agent 0.1 part.
- the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.
- the melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.
- Described compatibilizer is epoxy type compatibilizer, purchased from Zhejiang Hangzhou Xusheng New Material Technology Co., Ltd.
- the additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.
- a method for preparing a composite polymer material with strong impact resistance comprising the following steps:
- step (3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 120° C. to obtain a composite polymer material.
- the preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.15 parts of compatibilizer, auxiliary agent 0.5 servings.
- the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.
- the melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.
- the compatibilizer is an oxazoline-type chain extension compatibilizer, purchased from Shanghai Hanluo New Material Co., Ltd.
- the additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.
- a method for preparing a composite polymer material with strong impact resistance comprising the following steps:
- step 2 (3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 135° C. to obtain a composite polymer material.
- a composite polymer material with strong impact resistance and a preparation method thereof The specific steps are the same as those in Example 2, except that the auxiliary agent is a combination of talc powder and titanium dioxide.
- Izod unnotched impact strength according to the GB/T1843-2008 test standard, test the prepared composite polymer material at 23°C for the unnotched Izod impact strength.
- Biodegradation performance According to the GB/T19277 test standard, the biodegradation performance of the prepared composite polymer material is tested. The test environment temperature is 58 ⁇ 2°C, the humidity is 50-55%, 60 days after 12 months of forced composting , to observe the degradation state.
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Abstract
Disclosed is a composite polymer material with strong impact resistance. The composite polymer material is prepared from the following raw materials in parts by weight: 1-9 parts of a propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, and 0.05-0.2 parts of a compatilizer. By means of the synergistic effect of polycaprolactone having a crystallinity of 45% and the amorphous propylene glycol phthalate-propylene carbonate copolymer, the tensile strength and impact resistance of the composite polymer material are improved. Moreover, by means of adding the auxiliary agents of a talcum powder, titanium dioxide and castor oil, the forming effect of the composite polymer material is improved, and the use safety performance of the material is enhanced; and the material is particularly suitable for product packaging of foods and drugs. In addition, the composite polymer material has good oxygen and water vapor barrier properties, and also has good biodegradability and an excellent environmental protection performance.
Description
本申请要求于2021年12月08日提交中国专利局、申请号为CN202111492887.7、发明名称为“一种抗冲击能力强的复合高分子材料及其制备方法”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 December 08, 2021, with the application number CN202111492887.7, and the title of the invention "a composite polymer material with strong impact resistance and its preparation method", The entire contents of which are incorporated by reference in this application.
本发明涉及高分子化合物的组合物领域,涉及IPC分类号C08L(2006.01),具体涉及一种抗冲击能力强的复合高分子材料。The invention relates to the field of polymer compound compositions, and relates to an IPC classification number C08L (2006.01), in particular to a composite polymer material with strong impact resistance.
随着塑料聚合物在生活中的应用越来越广泛,随之带来的环境问题日趋严重,因此开发使用可降解的塑料聚合物替代传统塑料产品至关重要,但是由于可降解的塑料聚合物的原材料价格昂贵,生产成本较高,因此推广阻力较大,同时可降解塑料聚合物与其他聚合物的相容性不好还会导致产品力学性能的下降。As plastic polymers are more and more widely used in life, the ensuing environmental problems are becoming more and more serious. Therefore, it is very important to develop and use degradable plastic polymers to replace traditional plastic products. However, due to degradable plastic polymers The raw materials are expensive and the production cost is high, so the resistance to popularization is relatively large. At the same time, the poor compatibility of degradable plastic polymers with other polymers will also lead to a decline in the mechanical properties of the product.
中国发明专利CN202010814476.4公开了一种可降解塑料组合物,通过将PLA与PBS共混生成可降解的塑料组合物,但是PLA的价格昂贵,在实际生产过程中不容易推广使用。中国发明专利CN201210511722.4公开了一种具有超高韧性的完全降解型竹塑复合材料,通过引入天然植物纤维增加塑料基体间的韧性,但是天然植物纤维的加入会导致材料的成型效果变差,不适合吹膜工艺的生产,限制了部分产品的制备。Chinese invention patent CN202010814476.4 discloses a degradable plastic composition, which is produced by blending PLA and PBS. However, PLA is expensive, and it is not easy to popularize and use it in the actual production process. Chinese invention patent CN201210511722.4 discloses a fully degradable bamboo-plastic composite material with ultra-high toughness. The toughness between the plastic matrix is increased by introducing natural plant fibers, but the addition of natural plant fibers will lead to poor molding effect of the material. It is not suitable for the production of blown film process, which limits the preparation of some products.
发明内容Contents of the invention
为了增加复合高分子材料的抗冲击性能,提高复合材料的使用安全性,本发明提供了一种抗冲击能力强的复合高分子材料。In order to increase the impact resistance of the composite polymer material and improve the use safety of the composite material, the invention provides a composite polymer material with strong impact resistance.
本发明提供一种抗冲击能力强的复合高分子材料,制备原料以重量份计包括:邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物1-9份,聚己内酯1-9份,相容剂0.05-0.2份。The invention provides a composite polymer material with strong impact resistance. The preparation raw materials include, in parts by weight: 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, and Compatible agent 0.05-0.2 parts.
优选的,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的制备原料中含有环氧乙烷;Preferably, the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide;
所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的数均分子量为100000-200000g/mol。The number average molecular weight of the propylene glycol phthalate-propylene carbonate copolymer is 100000-200000 g/mol.
优选的,所述聚己内酯在160℃下的熔体流动速率为5.9-7.9g/10min。Preferably, the melt flow rate of the polycaprolactone at 160° C. is 5.9-7.9 g/10 min.
优选的,所述聚己内酯的数均分子量为80000-100000g/mol,含水率为0.3-0.4%,结晶度为43-48%。Preferably, the polycaprolactone has a number average molecular weight of 80000-100000 g/mol, a water content of 0.3-0.4%, and a crystallinity of 43-48%.
优选的,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物与聚己内酯的重量比为(1-7):(4-9)。Preferably, the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is (1-7):(4-9).
优选的,所述相容剂选自反应型扩链相容剂、接枝型相容剂和共聚型相容剂中的一种或几种的组合。Preferably, the compatibilizer is selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.
优选的,所述反应型扩链相容剂选自马来酸酐型相容剂、环氧型相容剂、丙烯酸型相容剂、氨基型相容剂、异氰酸酯型相容剂和噁唑啉型相容剂中的一种或几种的组合。Preferably, the reactive chain extension compatibilizer is selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic acid type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and oxazoline One or a combination of several types of compatibilizers.
优选的,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯与相容剂的重量比为1:(1-4):0.05。Preferably, in the propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone to the compatibilizer is 1:(1-4):0.05.
优选的,制备原料还包括助剂,重量份为0.1-1份。Preferably, the raw materials for preparation also include additives, in parts by weight of 0.1-1 parts.
优选的,所述助剂选自滑石粉、云母粉、石棉粉、二氧化钛、二氧化硅、硬脂酸、蓖麻油、聚乙烯蜡、白油中的一种或几种的组合。Preferably, the auxiliary agent is selected from one or a combination of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil.
优选的,所述助剂为滑石粉、二氧化钛和蓖麻油的组合。Preferably, the auxiliary agent is a combination of talcum powder, titanium dioxide and castor oil.
优选的,所述滑石粉、二氧化钛和蓖麻油的重量比为1:(0.5-1.2):(0.5-0.8)。Preferably, the weight ratio of the talcum powder, titanium dioxide and castor oil is 1:(0.5-1.2):(0.5-0.8).
本发明还提供了上述技术方案所述抗冲击能力强的复合高分子材料的制备方法,包括以下步骤:The present invention also provides a method for preparing a composite polymer material with strong impact resistance described in the above technical solution, comprising the following steps:
(1)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂在50-60℃下干燥3-5h;(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;
(2)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯,相容剂和助剂加入混合机中,80-120℃下混合搅拌3-10min;(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 3-10min at 80-120°C;
(3)将步骤2所得的混合料加入双螺杆挤出机中,100-160℃下,挤出造粒,得到复合高分子材料。(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.
本发明提供的抗冲击能力强的复合高分子材料,通过采用邻苯二甲酸 丙二醇酯-碳酸丙烯酯共聚物与聚己内酯(3-5):(5-7)的重量比,使复合高分子材料具有良好的氧气和水蒸气阻隔性,并且还具有良好的生物降解性,环保性能优良。The composite macromolecule material with strong impact resistance provided by the present invention, by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7), makes composite Polymer materials have good oxygen and water vapor barrier properties, and also have good biodegradability and excellent environmental performance.
本发明提供了一种抗冲击能力强的复合高分子材料,制备原料以重量份计包括:邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物1-9份,聚己内酯1-9份,相容剂0.05-0.2份。The invention provides a composite polymer material with strong impact resistance. The preparation raw materials include, in parts by weight, 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, 0.05-0.2 parts of compatibilizer.
在本发明中,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的制备原料中优选含有环氧乙烷,邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的数均分子量优选为100000-200000g/mol。In the present invention, preferably contain ethylene oxide in the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer, the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is preferably 100000- 200000g/mol.
申请人在实验过程中发现加入环氧乙烷制备得到的邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的分子量分布较窄,有利于提高复合高分子材料的加工成型性能,在改善加工性能的条件下,还能降低生产成本。During the experiment, the applicant found that the molecular weight distribution of the propylene glycol phthalate-propylene carbonate copolymer prepared by adding ethylene oxide is relatively narrow, which is conducive to improving the processing and molding performance of composite polymer materials. Under these conditions, the production cost can also be reduced.
在本发明中,所述聚己内酯在160℃下的熔体流动速率优选为5.9-7.9g/10min。In the present invention, the melt flow rate of the polycaprolactone at 160° C. is preferably 5.9-7.9 g/10 min.
在本发明中,所述聚己内酯的数均分子量优选为80000-100000g/mol,含水率优选为0.3-0.4%,结晶度优选为43-48%。In the present invention, the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol, the water content is preferably 0.3-0.4%, and the crystallinity is preferably 43-48%.
在本发明中,所述聚己内酯的数均分子量优选为80000-100000g/mol,含水率优选为0.35%,结晶度优选为45%。In the present invention, the number average molecular weight of the polycaprolactone is preferably 80000-100000 g/mol, the water content is preferably 0.35%, and the crystallinity is preferably 45%.
在本发明中,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物与聚己内酯的重量比优选为(1-7):(4-9),更优选为(3-5):(5-7),最优选为3:7。In the present invention, the weight ratio of the propylene glycol phthalate-propylene carbonate copolymer to polycaprolactone is preferably (1-7): (4-9), more preferably (3-5): (5-7), most preferably 3:7.
申请人在实验过程中进一步发现采用重量比为(3-5):(5-7)的邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物与聚己内酯的组合可以使复合高分子聚合物具有良好的水蒸气和氧气阻隔性能,可以最大程度上防止氧气与包装内物品接触,减少氧化变质。The applicant further finds that adopting weight ratio is (3-5): (5-7) the combination of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone can make composite macromolecular polymer It has good water vapor and oxygen barrier properties, which can prevent oxygen from contacting the packaged items to the greatest extent and reduce oxidative deterioration.
在本发明中,所述相容剂优选选自反应型扩链相容剂、接枝型相容剂、共聚型相容剂中的一种或几种的组合。In the present invention, the compatibilizer is preferably selected from one or a combination of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers.
在本发明中,所述反应型扩链相容剂优选选自马来酸酐型相容剂、环氧型相容剂、丙烯酸型相容剂、氨基型相容剂、异氰酸酯型相容剂和噁唑 啉型相容剂中的一种或几种的组合,更优选选自环氧型相容剂、异氰酸酯型相容剂和噁唑啉型相容剂中的一种或几种的组合。In the present invention, the reactive chain extension compatibilizer is preferably selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic type compatibilizer, amino type compatibilizer, isocyanate type compatibilizer and One or more combinations of oxazoline compatibilizers, more preferably one or more combinations selected from epoxy-type compatibilizers, isocyanate-type compatibilizers and oxazoline-type compatibilizers .
在本发明中,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯与相容剂的重量比优选为1:(1-4):(0.01-0.05)。In the present invention, in the propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone to the compatibilizer is preferably 1:(1-4):(0.01-0.05).
在本发明中,制备原料还优选包括助剂,重量份优选为0.1-1份。In the present invention, the raw materials for preparation preferably include auxiliary agents, and the parts by weight are preferably 0.1-1 parts.
在本发明中,所述助剂优选选自滑石粉、云母粉、石棉粉、二氧化钛、二氧化硅、硬脂酸、蓖麻油、聚乙烯蜡和白油中的一种或几种的组合,更优选为滑石粉,二氧化钛和蓖麻油的组合。在本发明中,所述滑石粉,二氧化钛和蓖麻油的重量比优选为1:(0.5-1.2):(0.5-0.8),更优选为1:1:0.7。In the present invention, the auxiliary agent is preferably selected from one or more combinations of talcum powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene wax and white oil, More preferred is a combination of talc, titanium dioxide and castor oil. In the present invention, the weight ratio of the talc powder, titanium dioxide and castor oil is preferably 1:(0.5-1.2):(0.5-0.8), more preferably 1:1:0.7.
申请人在实验过程中发现采用结晶度为45%的PCL与PPCP共混,加入滑石粉,二氧化钛和蓖麻油的助剂,可以使生成的复合高分子材料具有良好的抗冲击能力,并且具有良好的使用安全性。猜测可能的原因是,结晶度为45%的PCL与无定形PPCP共混,PPCP的分子链柔性较大,链间相互作用力较小,在反应过程中由于醚键的存在使分子链主链链段缠绕醚键从而发生内旋转,增大PCL链段的柔性,提高了复合材料的抗冲击能力。并且申请人在实验中进一步发现加入滑石粉,二氧化钛,蓖麻油提高了复合高分子材料的使用安全性,猜测可能的原因是,二氧化钛和蓖麻油的协同作用可以阻挡外界环境中的细菌到达食物的表面,减少食物的腐败变质,二氧化钛在复合材料中的流动性不好,蓖麻油的加入可以促进二氧化钛在复合材料中的移动,进一步增加使用安全效果。滑石粉与蓖麻油协同作用可以减弱PCL和PPCP之间的界面阻力,减少分子间的摩擦,提高PCL与PPCP之间的相容性,进一步提高抗冲击性能。During the experiment, the applicant found that blending PCL with PPCP with a crystallinity of 45% and adding talcum powder, titanium dioxide and castor oil as additives can make the resulting composite polymer material have good impact resistance and good impact resistance. safety of use. It is speculated that the possible reason is that PCL with a crystallinity of 45% is blended with amorphous PPCP. The molecular chain of PPCP is more flexible and the interaction force between chains is relatively small. The chain segment winds around the ether bond to generate internal rotation, which increases the flexibility of the PCL chain segment and improves the impact resistance of the composite material. And the applicant further found in the experiment that adding talcum powder, titanium dioxide, and castor oil improved the safety of the composite polymer material. It is speculated that the possible reason is that the synergistic effect of titanium dioxide and castor oil can prevent bacteria in the external environment from reaching food. On the surface, reduce the spoilage of food, the fluidity of titanium dioxide in the composite material is not good, the addition of castor oil can promote the movement of titanium dioxide in the composite material, and further increase the use safety effect. The synergistic effect of talc and castor oil can weaken the interfacial resistance between PCL and PPCP, reduce the friction between molecules, improve the compatibility between PCL and PPCP, and further improve the impact resistance.
本发明的第二个方面提供了一种抗冲击能力强的复合高分子材料的制备方法,包括以下步骤:A second aspect of the present invention provides a method for preparing a composite polymer material with strong impact resistance, comprising the following steps:
(1)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂在50-60℃下干燥3-5h;(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;
(2)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯,相容剂和助剂加入混合机中,80-120℃下混合搅拌3-10min;(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 3-10min at 80-120°C;
(3)将步骤2所得的混合料加入双螺杆挤出机中,100-160℃下,挤出造粒,得到复合高分子材料。(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.
与现有技术相比,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明所述抗冲击能力强的复合高分子材料,通过采用结晶度为45%的聚己内酯与无定形的邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物协同作用,提高了复合高分子材料的拉伸强度和抗冲击性能。(1) the strong composite macromolecular material of impact resistance of the present invention, by adopting crystallinity is the polycaprolactone of 45% and amorphous propylene glycol phthalate-propylene carbonate copolymer synergistic effect, has improved Tensile strength and impact resistance of composite polymer materials.
(2)本发明所述抗冲击能力强的复合高分子材料,通过加入滑石粉,二氧化钛,蓖麻油助剂,提高了复合高分子材料的成型效果,并且提高了材料的使用安全性能,尤其适合食品,药物的产品包装。(2) The composite polymer material with strong impact resistance of the present invention, by adding talcum powder, titanium dioxide, and castor oil additives, improves the molding effect of the composite polymer material, and improves the use safety performance of the material, and is especially suitable for Product packaging for food, medicine.
(3)本发明所述抗冲击能力强的复合高分子材料,通过采用邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物与聚己内酯(3-5):(5-7)的重量比,使复合高分子材料具有良好的氧气和水蒸气阻隔性,并且还具有良好的生物降解性,环保性能优良。(3) The composite polymer material with strong impact resistance of the present invention, by adopting the weight ratio of propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone (3-5): (5-7) , so that the composite polymer material has good oxygen and water vapor barrier properties, and also has good biodegradability and excellent environmental performance.
下面通过实施例对本发明进行具体描述。有必要在此指出的是,以下实施例只用于对本发明作进一步说明,不能理解为对本发明保护范围的限制,该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整,仍属于本发明的保护范围。The present invention is specifically described below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, some non-essential improvements made by those skilled in the art according to the content of the present invention above And adjustments still belong to the protection scope of the present invention.
另外,如果没有其它说明,所用原料都是市售得到的。In addition, all raw materials used are commercially available unless otherwise stated.
实施例1Example 1
一种抗冲击能力强的复合高分子材料,制备原料以重量份计包括:邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物3份,聚己内酯7份,相容剂0.05份,助剂0.1份。A composite polymer material with strong impact resistance, the preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.05 parts of compatibilizer, auxiliary agent 0.1 part.
所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的制备原料中含有环氧乙烷,邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的数均分子量为100000-200000g/mol,购自山东联创产业发展集团股份有限公司。The preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.
所述聚己内酯在160℃下的熔体流动速率为6.9g/10min,数均分子量为80000g/mol,含水率为0.35%,结晶度为45%,购自瑞典Perstorp,型号为2200。The melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.
所述相容剂为环氧型相容剂,购自浙江杭州旭昇新材料科技有限公 司。Described compatibilizer is epoxy type compatibilizer, purchased from Zhejiang Hangzhou Xusheng New Material Technology Co., Ltd.
所述助剂为滑石粉,二氧化钛和蓖麻油的组合,重量比为1:1:0.7。The additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.
一种抗冲击能力强的复合高分子材料的制备方法,包括以下步骤:A method for preparing a composite polymer material with strong impact resistance, comprising the following steps:
(1)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂在60℃下干燥4h;(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 60° C. for 4 hours;
(2)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯,相容剂和助剂加入混合机中,90℃下混合搅拌5min;(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 5 minutes at 90°C;
(3)将步骤(2)所得的混合料加入双螺杆挤出机中,120℃下,挤出造粒,得到复合高分子材料。(3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 120° C. to obtain a composite polymer material.
实施例2Example 2
一种抗冲击能力强的复合高分子材料,制备原料以重量份计包括:邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物3份,聚己内酯7份,相容剂0.15份,助剂0.5份。A composite polymer material with strong impact resistance. The preparation raw materials include in parts by weight: 3 parts of propylene glycol phthalate-propylene carbonate copolymer, 7 parts of polycaprolactone, 0.15 parts of compatibilizer, auxiliary agent 0.5 servings.
所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的制备原料中含有环氧乙烷,邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的数均分子量为100000-200000g/mol,购自山东联创产业发展集团股份有限公司。The preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide, and the number average molecular weight of propylene glycol phthalate-propylene carbonate copolymer is 100000-200000g/mol, purchased from Shandong Lianchuang Industrial Development Group Co., Ltd.
所述聚己内酯在160℃下的熔体流动速率为6.9g/10min,数均分子量为80000g/mol,含水率为0.35%,结晶度为45%,购自瑞典Perstorp,型号为2200。The melt flow rate of the polycaprolactone at 160° C. is 6.9 g/10 min, the number average molecular weight is 80,000 g/mol, the water content is 0.35%, and the crystallinity is 45%. It is purchased from Perstorp, Sweden, and the model is 2200.
所述相容剂为噁唑啉型扩链增容剂,购自上海瀚洛新材料有限公司。The compatibilizer is an oxazoline-type chain extension compatibilizer, purchased from Shanghai Hanluo New Material Co., Ltd.
所述助剂为滑石粉,二氧化钛和蓖麻油的组合,重量比为1:1:0.7。The additive is a combination of talcum powder, titanium dioxide and castor oil, with a weight ratio of 1:1:0.7.
一种抗冲击能力强的复合高分子材料的制备方法,包括以下步骤:A method for preparing a composite polymer material with strong impact resistance, comprising the following steps:
(1)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂在60℃下干燥4h;(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 60° C. for 4 hours;
(2)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯,相容剂和助剂加入混合机中,100℃下混合搅拌5min;(2) Add propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir for 5 minutes at 100°C;
(3)将步骤2所得的混合料加入双螺杆挤出机中,135℃下,挤出造粒,得到复合高分子材料。(3) Add the mixture obtained in step 2 into a twin-screw extruder, extrude and granulate at 135° C. to obtain a composite polymer material.
实施例3Example 3
一种抗冲击能力强的复合高分子材料及其制备方法,具体步骤同实施例2,不同点在于助剂为滑石粉和二氧化钛的组合。A composite polymer material with strong impact resistance and a preparation method thereof. The specific steps are the same as those in Example 2, except that the auxiliary agent is a combination of talc powder and titanium dioxide.
实施例4Example 4
一种抗冲击能力强的复合高分子材料及其制备方法,具体步骤同实施例2,不同点在于所述聚己内酯在160℃下的熔体流动速率为28g/10min,数均分子量为50000g/mol。A composite polymer material with strong impact resistance and a preparation method thereof, the specific steps are the same as in Example 2, the difference is that the melt flow rate of the polycaprolactone at 160°C is 28g/10min, and the number average molecular weight is 50000g/mol.
实施例5Example 5
一种抗冲击能力强的复合高分子材料及其制备方法,具体步骤同实施例2,不同点在于邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物6份,聚己内酯5份,相容剂0.2份。A composite polymer material with strong impact resistance and a preparation method thereof, the specific steps are the same as in Example 2, the difference lies in 6 parts of propylene glycol phthalate-propylene carbonate copolymer, 5 parts of polycaprolactone, compatible 0.2 parts of the agent.
性能测试Performance Testing
1.拉伸强度:依据GB/T1040.3-2006测试标准,测试制备得到的复合高分子材料的拉伸强度。1. Tensile strength: According to the GB/T1040.3-2006 test standard, the tensile strength of the prepared composite polymer material was tested.
2.悬臂梁无缺口冲击强度:依据GB/T1843-2008测试标准,测试制备得到的复合高分子材料在23℃下的悬臂梁无缺口冲击强度。2. Izod unnotched impact strength: according to the GB/T1843-2008 test standard, test the prepared composite polymer material at 23°C for the unnotched Izod impact strength.
3.生物降解性能:依据GB/T19277测试标准,测试制备得到的复合高分子材料的生物降解性能,测试环境温度为58±2℃,湿度为50-55%,60天强制堆肥12个月后,观察降解状态。3. Biodegradation performance: According to the GB/T19277 test standard, the biodegradation performance of the prepared composite polymer material is tested. The test environment temperature is 58±2°C, the humidity is 50-55%, 60 days after 12 months of forced composting , to observe the degradation state.
将实施例依据上述标准进行测试,结果见于表1。The examples were tested according to the above-mentioned standards, and the results are shown in Table 1.
表1Table 1
the | 拉伸强度/MPaTensile strength/MPa | 悬臂梁缺口冲击强度kJ/m 2 Izod notched impact strength kJ/m 2 | 生物降解性biodegradability |
实施例1Example 1 | >35>35 | 80.580.5 | 完全降解Completely degraded |
实施例2Example 2 | >39>39 | 82.182.1 | 完全降解Completely degraded |
实施例3Example 3 | 3030 | 74.274.2 | 完全降解Completely degraded |
实施例4Example 4 | 2828 | 72.672.6 | 完全降解Completely degraded |
实施例5Example 5 | 2929 | 73.573.5 | 完全降解Completely degraded |
以上所述仅是本发明的优选实施方式,应当指出,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, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
Claims (13)
- 一种抗冲击能力强的复合高分子材料,其特征在于,制备原料以重量份计包括:邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物1-9份,聚己内酯1-9份,相容剂0.05-0.2份。A composite polymer material with strong impact resistance is characterized in that the preparation raw materials include in parts by weight: 1-9 parts of propylene glycol phthalate-propylene carbonate copolymer, 1-9 parts of polycaprolactone, 0.05-0.2 parts of compatibilizer.
- 根据权利要求1所述抗冲击能力强的复合高分子材料,其特征在于,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的制备原料中含有环氧乙烷;According to the strong composite polymer material of impact resistance described in claim 1, it is characterized in that, the preparation raw material of described propylene glycol phthalate-propylene carbonate copolymer contains ethylene oxide;所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物的数均分子量为100000-200000g/mol。The number average molecular weight of the propylene glycol phthalate-propylene carbonate copolymer is 100000-200000 g/mol.
- 根据权利要求1或2所述抗冲击能力强的复合高分子材料,其特征在于,所述聚己内酯在160℃下的熔体流动速率为5.9-7.9g/10min。The composite polymer material with strong impact resistance according to claim 1 or 2, characterized in that the melt flow rate of the polycaprolactone at 160°C is 5.9-7.9g/10min.
- 根据权利要求1或2所述抗冲击能力强的复合高分子材料,其特征在于,所述聚己内酯的数均分子量为80000-100000g/mol,含水率为0.3-0.4%,结晶度为43-48%。The composite polymer material with strong impact resistance according to claim 1 or 2 is characterized in that the number average molecular weight of the polycaprolactone is 80000-100000g/mol, the water content is 0.3-0.4%, and the crystallinity is 43-48%.
- 根据权利要求1所述抗冲击能力强的复合高分子材料,其特征在于,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物与聚己内酯的重量比为(1-7):(4-9)。The strong composite macromolecular material of impact resistance according to claim 1, is characterized in that, the weight ratio of described propylene glycol phthalate-propylene carbonate copolymer and polycaprolactone is (1-7):( 4-9).
- 根据权利要求1所述抗冲击能力强的复合高分子材料,其特征在于,所述相容剂选自反应型扩链相容剂、接枝型相容剂和共聚型相容剂中的一种或几种的组合。The composite polymer material with strong impact resistance according to claim 1, wherein the compatibilizer is selected from one of reactive chain extension compatibilizers, grafting compatibilizers and copolymerization compatibilizers one or a combination of several.
- 根据权利要求6所述抗冲击能力强的复合高分子材料,其特征在于,所述反应型扩链相容剂选自马来酸酐型相容剂、环氧型相容剂、丙烯酸型相容剂、氨基型相容剂、异氰酸酯型相容剂和噁唑啉型相容剂中的一种或几种的组合。According to the composite polymer material with strong impact resistance according to claim 6, it is characterized in that, the reactive chain extension compatibilizer is selected from maleic anhydride type compatibilizer, epoxy type compatibilizer, acrylic acid type compatibilizer One or more combinations of compatibilizers, amino-type compatibilizers, isocyanate-type compatibilizers and oxazoline-type compatibilizers.
- 根据权利要求1所述抗冲击能力强的复合高分子材料,其特征在于,所述邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯与相容剂的重量比为1:(1-4):0.05。The strong composite macromolecular material of impact resistance according to claim 1, is characterized in that, described propylene glycol phthalate-propylene carbonate copolymer, the weight ratio of polycaprolactone and compatibilizer is 1:( 1-4): 0.05.
- 根据权利要求1所述抗冲击能力强的复合高分子材料,其特征在于, 制备原料还包括助剂,重量份为0.1-1份。The composite polymer material with strong impact resistance according to claim 1, characterized in that the preparation raw materials further include additives, the parts by weight are 0.1-1 parts.
- 根据权利要求9所述抗冲击能力强的复合高分子材料,其特征在于,所述助剂选自滑石粉、云母粉、石棉粉、二氧化钛、二氧化硅、硬脂酸、蓖麻油、聚乙烯蜡和白油中的一种或几种的组合。The composite polymer material with strong impact resistance according to claim 9, wherein the auxiliary agent is selected from talc powder, mica powder, asbestos powder, titanium dioxide, silicon dioxide, stearic acid, castor oil, polyethylene One or a combination of waxes and white oils.
- 根据权利要求10所述抗冲击能力强的复合高分子材料,其特征在于,所述助剂为滑石粉、二氧化钛和蓖麻油的组合。The composite polymer material with strong impact resistance according to claim 10, characterized in that the additive is a combination of talcum powder, titanium dioxide and castor oil.
- 根据权利要求11所述抗冲击能力强的复合高分子材料,其特征在于,所述滑石粉、二氧化钛和蓖麻油的重量比为1:(0.5-1.2):(0.5-0.8)。The composite polymer material with strong impact resistance according to claim 11, characterized in that the weight ratio of the talcum powder, titanium dioxide and castor oil is 1:(0.5-1.2):(0.5-0.8).
- 权利要求9~11任一项所述抗冲击能力强的复合高分子材料的制备方法,其特征在于,包括以下步骤:The method for preparing a composite polymer material with strong impact resistance according to any one of claims 9 to 11, characterized in that it comprises the following steps:(1)将邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂在50-60℃下干燥3-5h;(1) Dry propylene glycol phthalate-propylene carbonate copolymer, polycaprolactone and compatibilizer at 50-60°C for 3-5h;(2)将步骤(1)干燥后的邻苯二甲酸丙二醇酯-碳酸丙烯酯共聚物,聚己内酯和相容剂与助剂加入混合机中,80-120℃下混合搅拌3-10min;(2) Add the dried propylene phthalate-propylene carbonate copolymer, polycaprolactone, compatibilizer and auxiliary agent into the mixer, and mix and stir at 80-120°C for 3-10min ;(3)将步骤(2)所得的混合料加入双螺杆挤出机中,100-160℃下,挤出造粒,得到复合高分子材料。(3) Add the mixture obtained in step (2) into a twin-screw extruder, extrude and granulate at 100-160° C. to obtain a composite polymer material.
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