WO2024066971A1 - 一种聚丙烯微发泡材料及其制备方法和应用 - Google Patents

一种聚丙烯微发泡材料及其制备方法和应用 Download PDF

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WO2024066971A1
WO2024066971A1 PCT/CN2023/117137 CN2023117137W WO2024066971A1 WO 2024066971 A1 WO2024066971 A1 WO 2024066971A1 CN 2023117137 W CN2023117137 W CN 2023117137W WO 2024066971 A1 WO2024066971 A1 WO 2024066971A1
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polypropylene
parts
foaming
foam material
polypropylene micro
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PCT/CN2023/117137
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English (en)
French (fr)
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俞飞
陈平绪
叶南飚
吴国峰
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金发科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to the field of polypropylene materials, in particular to a polypropylene micro-foam material and a preparation method and application thereof.
  • Polypropylene is a crystalline polymer with a regular structure, usually in the form of white granules or powders. It is an odorless, non-toxic, lightweight thermoplastic resin. Polypropylene has the advantages of easy processing, good impact strength, flexibility, and electrical insulation, and has good chemical resistance. It is widely used in the automotive industry, household appliances, electronics, packaging, building materials, and furniture.
  • Expanded polypropylene is a semi-high crystalline polymer/gas composite material with excellent performance. With its unique and superior performance, it has become the fastest growing new environmentally friendly pressure-resistant buffering and heat-insulating material. EPP products have excellent shock absorption performance, high recovery rate after deformation, good heat resistance, chemical resistance, oil resistance and heat insulation. At the same time, its light weight can greatly reduce the weight of the goods.
  • EPP is also an environmentally friendly material, which is prone to ⁇ -degradation, and PP foam is easy to recycle. Its environmental friendliness is better than other foam materials, so it is called “green” foam. It is precisely because of the excellent performance of expanded polypropylene that it has become a new type of foam material with greater application value and market potential after polystyrene (EPS) and polyurethane (EPU) foam materials.
  • EPS polystyrene
  • EPU polyurethane
  • the existing expanded polypropylene materials have defects such as orange peel appearance, poor cell uniformity, and easy pore merging and pore breakage.
  • the purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a polypropylene micro-foam material and its preparation method and application.
  • the polypropylene micro-foam material is extruded and foamed by adding a foaming agent, and the obtained product has a good appearance, dense and uniform pores, a closed cell rate of more than 92%, and a high weight reduction ratio of the product obtained after foaming.
  • the technical scheme adopted by the present invention is: a polypropylene micro-foam material, comprising the following components by weight: 45-96 parts of polypropylene, 1-5 parts of poly 1-butene grafted sodium maleate, 2-10 parts of ethylene-octene random copolymer, 3-40 parts of filler, 0.1-0.4 parts of lubricant, 0.1-0.4 parts of antioxidant share;
  • the melting index of the polypropylene under the test conditions of 230°C and 2.16kg is 0.5-3g/10min, which is implemented in accordance with the test standard ISO 1133-1/2:2012; if the melting index of the polypropylene is too low, its melt strength is too high, which will lead to poor foaming effect, while if the melting index is too high, its melt strength is too low, which will lead to defects such as bubble rupture and combined holes.
  • the melt index of the ethylene-octene random copolymer under the test conditions of 190°C and 2.16kg is 5-13g/10min, which is carried out according to the test standard ISO 1133-1/2:2012.
  • Octene has a large molecular weight and good entanglement effect with polypropylene, which is conducive to foaming without insufficient ductility and pores. Too high a melt index of the ethylene-octene random copolymer leads to foaming and pores, and too low a melt index leads to poor foaming effect.
  • the polypropylene micro-foam material comprises the following components in parts by weight: 53-62 parts of polypropylene, 2-3 parts of poly-1-butene grafted sodium maleate, 5-7 parts of ethylene-octene random copolymer, 10-30 parts of filler, 0.1-0.4 parts of lubricant, and 0.1-0.4 parts of antioxidant;
  • the filler is at least one of talc, calcium carbonate, and basic magnesium sulfate whiskers.
  • the lubricant is a stearate.
  • the antioxidant is hindered phenols and/or phosphites.
  • the present application adopts poly 1-butene grafted sodium maleate, which has a melting point of 104°C, much lower than that of ordinary polypropylene grafted maleic anhydride (melting point 165°C). Its special low melting point and polar grafting modification can significantly improve the interfacial bonding strength between the filler and polypropylene, solve the problems of uneven pores and broken pores, and is more conducive to foaming molding.
  • the poly-1-butene grafted sodium maleate is prepared by the following method: poly-1-butene, sodium maleate, and an antioxidant are mixed uniformly to obtain a mixture; an initiator, ⁇ -methylstyrene (AMS), and 1-octene are dissolved in acetone, and then mixed uniformly with the mixture, and after the acetone is volatilized, a melt extrusion grafting reaction is performed to obtain poly-1-butene grafted sodium maleate.
  • the grafting rate of the poly-1-butene grafted sodium maleate is 0.8-1.5%.
  • the initiator is di-tert-butyl peroxide (DTBP).
  • DTBP di-tert-butyl peroxide
  • the antioxidant is a hindered phenol and/or phosphite antioxidant.
  • the amounts of the components used in the preparation process of the poly 1-butene grafted sodium maleate are: 100 parts of poly-1-butene, 1.5-4.5 parts of sodium maleate, 0.2-0.4 parts of antioxidant, 0.2-0.4 parts of initiator, 2-3 parts of ⁇ -methylstyrene, and 1-1.5 parts of 1-octene.
  • the melt extrusion adopts a twin-screw extruder at a temperature of 135-150°C.
  • the poly 1-butene grafted sodium maleate is purified by the following method: The poly(1-butene) grafted sodium maleate is dissolved in xylene, and then precipitated with acetone, washed and dried to obtain a first purified product; the above purification process is repeated to obtain purified poly(1-butene) grafted sodium maleate.
  • the preparation method of the polypropylene micro-foam material comprises the following steps: uniformly mixing the components, melt-extruding and granulating, adding a foaming agent, and extruding and foaming to obtain.
  • the melt extrusion granulation adopts a 75D co-rotating twin-screw extruder, and the temperature from the feeding section to the die is 170°C, 200°C, 200°C, 210°C, 210°C, 205°C, 205°C, 200°C, and 200°C respectively.
  • the added amount of the foaming agent is 1-3%.
  • polypropylene micro-foam material is used in the preparation of pressure-resistant, buffering and heat-insulating materials, such as car seat side guards, car trunk spare tire covers, etc.
  • the present invention can ensure that the material can be smoothly foamed by compounding polypropylene with a suitable melt index and ethylene-octene random copolymer.
  • poly 1-butene grafted sodium maleate is added, and its special low melting point and polar graft modification can significantly improve the interface bonding force between the filler and the polypropylene, which is more conducive to foaming molding.
  • the polypropylene micro-foam material is added with a foaming agent for extrusion foaming, and the obtained product has a good appearance, dense and uniform pores, reaching the first level, a closed cell rate of up to 92.3%-94.3%, a weight reduction ratio of 22.7%-27.2%, and a density of 0.661-0.928g/ cm3 after foaming.
  • the polypropylene micro-foam material of the present invention has a simple preparation process and is suitable for mass production.
  • antioxidants and lubricants are commercially available, and the same antioxidants and lubricants are used in parallel experiments.
  • melt index of the following PP is tested using the test standard ISO 1133-1/2:2012 at 230°C and 2.16kg.
  • melt index of the following ethylene-octene random copolymer is tested using the test standard ISO 1133-1/2:2012 at 190°C and 2.16 kg.
  • PP-1 B8101 (copolymer, melt index 0.5g/10min), supplier: Yanshan Petrochemical;
  • PP-2 K8303 (copolymer, melt index 3g/10min), supplier: Yanshan Petrochemical;
  • PP-3 EP548R (copolymer, melt index 30g/10min), supplier: CNOOC Shell;
  • PP-4 R4220 (copolymer, melt index 0.3g/10min), supplier: Yanshan Petrochemical;
  • PC-1 Polypropylene grafted with maleic anhydride: PC-1, supplier: Foshan Nanhai Bochen;
  • Talc AH-51210, 3000 mesh, supplier: Liaoning Aihai;
  • Ethylene-octene random copolymer 8842 (melt index 1g/10min), supplier: Dow Chemical, USA;
  • Ethylene-octene random copolymer 8200 (melt index 5g/10min), supplier: Dow Chemical, USA;
  • Ethylene-octene random copolymer 8407 (melt index 30 g/10 min), supplier: Dow Chemical, USA;
  • Ethylene-octene random copolymer 8137 (melt index 13 g/10 min), supplier: Dow Chemical, USA;
  • Thermoplastic elastomer SEBS G1657, supplier: Dow Chemical, USA;
  • Hindered phenol antioxidant SONOX 1010, commercially available
  • Phosphite antioxidant SONOX 168, commercially available
  • Zinc stearate BS-2818, commercially available;
  • Inorganic foaming agent EE25C, supplier: Japan Yonghe Fine Chemicals;
  • Poly 1-butene grafted sodium maleate (PB-1-g-sodium maleate): prepared by the following method: poly-1-butene, sodium maleate, and antioxidant 168 are mixed uniformly to obtain a mixture; initiator di-tert-butyl peroxide (DTBP), ⁇ -methylstyrene (AMS), and 1-octene are dissolved in acetone, and then mixed uniformly with the mixture; after the acetone is volatilized, a twin-screw extruder is used to melt extrude and graft at 150°C to obtain poly 1-butene grafted sodium maleate; the amount of each component is: 100 parts of poly-1-butene, 3 parts of sodium maleate, 0.3 parts of antioxidant, 0.2 parts of di-tert-butyl peroxide, 3 parts of ⁇ -methylstyrene, and 1.5 parts of 1-octene.
  • DTBP initiator di-tert-butyl peroxide
  • AMS ⁇ -methylst
  • the obtained poly 1-butene grafted sodium maleate is purified: the poly 1-butene grafted sodium maleate is dissolved in xylene, precipitated with acetone, washed and dried to obtain the first purified product; the above purification is repeated twice to obtain the purified poly 1-butene grafted sodium maleate (grafting rate is 1.2%), which is used to prepare polypropylene micro-foam material.
  • Appearance Observe the surface of a 100*100mm square plate with naked eyes and count the number of orange peel-like defects; Excellent: 0 orange peel; Good: 1-3 orange peels; Fair: 4-6 orange peels;
  • Cell density and uniformity Test the cell size of a 100*100mm square plate according to GB/T 12811-1991; Level 1: 0-20 ⁇ m; Level 2: 21-40 ⁇ m; Level 3: 41-60 ⁇ m; Level 4: 61-80 ⁇ m; Level 5: 81-100 ⁇ m; Level 6: 101-120 ⁇ m; Level 7: 121-140 ⁇ m; No foaming; Pores;
  • Weight reduction ratio [(density before foaming - density after foaming)/density before foaming]*100%
  • the polypropylene micro-foam material of comparative example 1 does not add poly 1-butene grafted sodium maleate, and the weight loss ratio and closed cell rate of the product are significantly lower than those of Example 1, the uniformity of the pore density is poor, and the appearance is average;
  • the polypropylene micro-foam material of comparative example 2 uses polypropylene with a melt index of 30g/10min for extrusion foaming, and the weight loss ratio and closed cell rate of the product are much lower than those of Example 1, the uniformity of the pore density is poor, and the appearance is good;
  • the polypropylene micro-foam material of comparative example 3 uses polypropylene grafted maleic anhydride to replace poly 1-butene grafted sodium maleate, and the weight loss ratio and closed cell rate of the product are significantly lower than those of Example 1, the uniformity of the pore density is poor, and the appearance is average;
  • comparative examples 4 and 5 use ethylene-butene random copolymers with melt indexes of 1
  • the uniformity is poor; in comparative example 6, SEBS is used to replace the ethylene-octene random copolymer, and the product has shrinkage holes in appearance, and the uniformity of pore density is poor; in comparative example 7, the amount of PB-1-g-sodium maleate used is too small, and the weight loss ratio and closed cell rate of the product are lower than those in Example 1, the appearance is good, and the uniformity of pore density is poor; in comparative example 8, the amount of ethylene-octene random copolymer used is too small, and the weight loss ratio and closed cell rate of the product are lower than those in Example 1, the appearance is good, and the uniformity of pore density is poor; in comparative example 8, too much poly 1-butene sodium maleate is used, and the weight loss ratio and closed cell rate of the product are significantly lower than those in Example 1, the uniformity of pore density is poor, and the appearance is general; in comparative example 9, too much poly 1-butene grafted sodium maleate is used, the uniformity of pore density is

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Abstract

本发明公开了一种聚丙烯微发泡材料及其制备方法和应用。聚丙烯微发泡材料包括以下组分：聚丙烯、聚1-丁烯接枝马来酸钠、乙烯-辛烯无规共聚物、填料、润滑剂、抗氧剂。本发明通过采用合适熔融指数的聚丙烯与乙烯-辛烯无规共聚物复配，保证材料可以顺利发泡，在此基础上添加聚1-丁烯接枝马来酸钠，其特殊的低熔点以及极性接枝改性明显提高填料与聚丙烯的界面结合力，更有利于发泡成型；将聚丙烯微发泡材料添加发泡剂挤出发泡，得到的制品外观良好，泡孔致密均匀，达到一级，闭孔率高达92.3％-94.3％，制品减重比例达到22.7％-27.2％，发泡后密度达到0.661-0.928g/cm3。

Description

一种聚丙烯微发泡材料及其制备方法和应用 技术领域
本发明涉及聚丙烯材料领域，尤其是一种聚丙烯微发泡材料及其制备方法和应用。
背景技术
聚丙烯(PP)是一种结构规整的结晶性聚合物，常为白色粒料或粉料，是无味、无毒、质轻的热塑性树脂。聚丙烯具备易加工、冲击强度、挠曲性以及电绝缘性好等优点，并具有良好的耐化学性能，在汽车工业、家用电器、电子、包装、建材及家具等方面具有广泛的应用。
随着汽车等行业的轻量化发展趋势，发泡成为了轻量化的重要途径之一，其中聚丙烯微发泡得到广泛青睐，在内饰和外饰件上获得了深入研究，如门板、内门把手、座椅导轨护板等零部件。发泡聚丙烯材料(EPP，Expanded Polypropylene)是一种性能优异的半高结晶型聚合物/气体复合材料，以其独特而优越的性能成为目前增长最快的新型环保抗压缓冲隔热材料。EPP制品具有十分优异的抗震吸能性能、形变后回复率高、很好的耐热性、耐化学品、耐油性和隔热性等优点；同时，其质量轻，可大幅度减轻物品质量；另外，EPP还是一种环保材料，易于发生β降解，且PP泡沫便于回收利用，其环境友好性优于其他泡沫材料，因而被称为“绿色”泡沫。正是由于发泡聚丙烯材料表现出来的优异性能，使其成为继聚苯乙烯(EPS)、聚氨酯(EPU)泡沫材料之后更具应用价值和市场潜力的新型泡沫材料，但是现有发泡聚丙烯材料存在外观橘皮、泡孔均匀性差、容易并孔&破孔等缺陷。
发明内容
基于此，本发明的目的在于克服上述现有技术的不足之处，提供一种聚丙烯微发泡材料及其制备方法和应用。该种聚丙烯微发泡材料经添加发泡剂挤出发泡，得到的制品外观良好，泡孔致密均匀，闭孔率高达92％以上，并且发泡后得到的制品减重比例高。
为实现上述目的，本发明所采取的技术方案为：一种聚丙烯微发泡材料，包括以下重量份计的组分：聚丙烯45～96份、聚1-丁烯接枝马来酸钠1～5份、乙烯-辛烯无规共聚物2～10份、填料3～40份、润滑剂0.1～0.4份、抗氧剂0.1～0.4 份；
所述聚丙烯在230℃、2.16kg测试条件下的熔融指数为0.5-3g/10min，按照测试标准ISO 1133-1/2:2012执行；聚丙烯的熔融指数过低其熔体强度过高会导致发泡效果差，熔融指数过高其熔体强度过低会导致泡孔破裂、并孔等缺陷。
所述乙烯-辛烯无规共聚物在190℃、2.16kg测试条件下的熔融指数为5-13g/10min，按照测试标准ISO 1133-1/2:2012执行。辛烯的分子量大，与聚丙烯缠结效果好，有利于发泡而不至于延展性不足而破孔。乙烯-辛烯无规共聚物熔融指数过高导致发泡并孔，熔融指数过低导致发泡效果差。
优选地，所述聚丙烯微发泡材料，包括以下重量份计的组分：聚丙烯53～62份、聚1-丁烯接枝马来酸钠2～3份、乙烯-辛烯无规共聚物5～7份、填料10～30份、润滑剂0.1～0.4份、抗氧剂0.1～0.4份；
优选地，所述填料为滑石粉、碳酸钙、碱式硫酸镁晶须中的至少一种。
优选地，所述润滑剂为硬脂酸盐类。
优选地，所述抗氧剂为受阻酚类和/或亚磷酸酯类。
本申请采用聚1-丁烯接枝马来酸钠，其熔点为104℃，比普通的聚丙烯接枝马来酸酐(熔点165℃)熔点低很多，其特殊的低熔点以及极性接枝改性可以明显提高填料与聚丙烯的界面结合力，解决泡孔不均一、破孔的问题，更有利于发泡成型。
优选地，所述聚1-丁烯接枝马来酸钠通过如下方法制备得到：将聚-1丁烯、马来酸钠、抗氧剂混合均匀，得到混合物；将引发剂、α-甲基苯乙烯(AMS)、1-辛烯溶解于丙酮中，再与所述混合物混合均匀，待丙酮挥发后进行熔融挤出接枝反应，得到聚1-丁烯接枝马来酸钠。上述聚1-丁烯接枝马来酸钠的接枝率为0.8～1.5％。
优选地，所述引发剂为二叔丁基过氧化物(DTBP)。
优选地，所述抗氧剂为受阻酚和/或亚磷酸酯类抗氧剂。
优选地，所述聚1-丁烯接枝马来酸钠制备过程中各组分用量为：聚-1丁烯100份、马来酸钠1.5～4.5份、抗氧剂0.2～0.4份、引发剂0.2～0.4份、α-甲基苯乙烯2～3份、1-辛烯1～1.5份。
优选地，所述熔融挤出采用双螺杆挤出机，温度为135～150℃。
优选地，所述聚1-丁烯接枝马来酸钠采用以下方法进行纯化：将聚1-丁烯接 枝马来酸钠溶解于二甲苯，再采用丙酮沉淀并洗涤沉淀，干燥，得到第一次纯化物；重复上述纯化过程，得到纯化后的聚1-丁烯接枝马来酸钠。
上述聚丙烯微发泡材料的制备方法，包括以下步骤：将各组分混合均匀，熔融挤出造粒，加入发泡剂，挤出发泡，得到。
优选地，所述熔融挤出造粒采用75D同向双螺杆挤出机，温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。
优选地，所述发泡剂的添加量为1～3％。
上述聚丙烯微发泡材料在制备抗压缓冲隔热材料中的应用，例如汽车座椅侧护板、汽车后备箱备胎盖板等。
相对于现有技术，本发明的有益效果为：
本发明通过采用合适熔融指数的聚丙烯与乙烯-辛烯无规共聚物复配，可以保证材料可以顺利发泡，在此基础上添加聚1-丁烯接枝马来酸钠，其特殊的低熔点以及极性接枝改性可以明显提高填料与聚丙烯的界面结合力，更有利于发泡成型。将聚丙烯微发泡材料添加发泡剂挤出发泡，得到的制品外观良好，泡孔致密均匀，达到一级，闭孔率高达92.3％-94.3％，制品减重比例达到22.7％-27.2％，发泡后密度达到0.661-0.928g/cm3。本发明的聚丙烯微发泡材料制备工艺简单，适合大批量生产。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
实施例中，所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
下述实施例和对比例中，如无特别说明，抗氧剂、润滑剂均通过市售获得，且平行实验中使用的是相同的抗氧剂、润滑剂。
下述PP的熔融指数采用测试标准ISO 1133-1/2:2012，在230℃、2.16kg测试条件下进行测试。
下述乙烯-辛烯无规共聚物的熔融指数采用测试标准ISO 1133-1/2:2012，在190℃、2.16kg测试条件下进行测试。
实施例及对比例所用原料如下：
PP-1：B8101(共聚，熔融指数0.5g/10min)，供应商：燕山石化；
PP-2：K8303(共聚，熔融指数3g/10min)，供应商：燕山石化；
PP-3：EP548R(共聚，熔融指数30g/10min)，供应商：中海壳牌；
PP-4：R4220(共聚，熔融指数0.3g/10min)，供应商：燕山石化；
聚丙烯接枝马来酸酐：PC-1，供应商：佛山南海柏晨；
碳酸钙：75T，供应商：长兴欧米亚；
碱式硫酸镁晶须：WS-1S2，供应商：营口康如科技；
滑石粉：AH-51210，3000目，供应商：辽宁艾海；
乙烯-辛烯无规共聚物：8842(熔融指数1g/10min)，供应商：美国陶氏化学；
乙烯-辛烯无规共聚物：8200(熔融指数5g/10min)，供应商：美国陶氏化学；
乙烯-辛烯无规共聚物：8407(熔融指数30g/10min)，供应商：美国陶氏化学；
乙烯-辛烯无规共聚物：8137(熔融指数13g/10min)，供应商：美国陶氏化学；
热塑性弹性体SEBS：G1657，供应商：美国陶氏化学；
受阻酚类抗氧剂：SONOX 1010，市售；
亚磷酸酯类抗氧剂：SONOX 168，市售；
硬脂酸锌：BS-2818，市售；
无机发泡剂：EE25C，供应商：日本永和精细化工；
聚1-丁烯接枝马来酸钠(PB-1-g-马来酸钠)：通过如下方法制备：将聚-1丁烯、马来酸钠、抗氧剂168混合均匀，得到混合物；将引发剂二叔丁基过氧化物(DTBP)、α-甲基苯乙烯(AMS)、1-辛烯溶解于丙酮中，再与所述混合物混合均匀，待丙酮挥发后采用双螺杆挤出机150℃熔融挤出接枝反应，得到聚1-丁烯接枝马来酸钠；各组分用量为：聚-1丁烯100份、马来酸钠3份、抗氧剂0.3份、二叔丁基过氧化物0.2份、α-甲基苯乙烯3份、1-辛烯1.5份。得到的聚1-丁烯接枝马来酸钠进行纯化：将聚1-丁烯接枝马来酸钠溶解于二甲苯，再采用丙酮沉淀并洗涤沉淀，干燥，得到第一次纯化物；重复上述纯化2次，得到纯化后的聚1-丁烯接枝马来酸钠(接枝率为1.2％)，将其用于的制备聚丙烯微发泡材料。
实施例及对比例
实施例及对比例的聚丙烯微发泡材料，组分及用量、性能如表1和表2所示。
实施例和对比例的聚丙烯微发泡材料制备方法包括如下步骤：
将发泡剂之外的各组分加入高速混合机中，混合3分钟，其中高速混合机的转速为800转/分钟。将混合好的组分加入75D同向双螺杆挤出机中，熔融挤出造粒，干燥，冷却，得到的聚丙烯微发泡材料；双螺杆挤出机的温度从喂料段到机头依次为170℃、200℃、200℃、210℃、210℃、205℃、205℃、205℃、200℃、200℃。将聚丙烯微发泡材料与2％的无机发泡剂混合均匀，加入到挤出机中进行发泡挤出，注塑成100*100*2mm方板，进行性能测试。
性能测试
实施例及对比例的制品进行性能测试，具体测试方法如下：
外观：肉眼观察100*100mm的方板表面，计数橘皮样不良外观数量；优：出现0处橘皮；良：1-3处橘皮；一般：4-6处橘皮；
泡孔致密均匀性：将100*100mm的方板按照GB/T 12811-1991测试泡孔尺寸；一级：0-20μm；二级：21-40μm；三级：41-60μm；四级：61-80μm；五级：81-100μm；六级：101-120μm；七级121-140μm；无法发泡；破孔；
密度：按照ISO 1183-1:2019进行测试；
减重比例：[(发泡前密度-发泡后密度)/发泡前密度]*100％；
闭孔率：按照GB 10799-2008进行测试。
表1

表2

结果表明，对比例1的聚丙烯微发泡材料不添加聚1-丁烯接枝马来酸钠，制品减重比例和闭孔率明显小于实施例1，泡孔致密均匀性不佳，外观一般；对比例2的聚丙烯微发泡材料采用熔融指数为30g/10min的聚丙烯进行挤出发泡，制品减重比例和闭孔率远小于实施例1，泡孔致密均匀性不佳，外观良；对比例3的聚丙烯微发泡材料采用聚丙烯接枝马来酸酐替换聚1-丁烯接枝马来酸钠，制品减重比例和闭孔率明显不及实施例1，泡孔致密均匀性不佳，外观一般；对比例4和5采用熔融指数为1g/10min、30g/10min的乙烯-丁烯无规共聚物，制品减重比例和闭孔率低于实施例1，外观良，对比例4泡孔致密均匀性不佳，对比例5泡孔致密均匀性不佳；对比例6采用SEBS替换乙烯-辛烯无规共聚物，制品外观缩孔，泡孔致密均匀性不佳；对比例7采用的PB-1-g-马来酸钠用量过少，制品减重比例和闭孔率低于实施例1，外观良，泡孔致密均匀性不佳；对比例8采用的乙烯-辛烯无规共聚物用量过少，制品减重比例和闭孔率低于实施例1，外观良，泡孔致密均匀性不佳；对比例8采用的聚1-丁烯马来酸钠用量过多，制品减重比例和闭孔率明显小于实施例1，泡孔致密均匀性不佳，外观一般；对比例9采用的聚1-丁烯接枝马来酸钠用量过多，泡孔致密均匀性不佳，外观一般；对比例10采用熔融指数为0.3g/10min的聚丙烯进行挤出发泡，成型困难，制品减重比例小、闭孔率低。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本 发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (8)

  1. 一种聚丙烯微发泡材料，其特征在于，包括以下重量份计的组分：聚丙烯45～96份、聚1-丁烯接枝马来酸钠1～5份、乙烯-辛烯无规共聚物2～10份、填料3～40份、润滑剂0.1～0.4份、抗氧剂0.1～0.4份；
    所述聚丙烯的熔融指数为0.5-3g/10min；
    所述乙烯-辛烯无规共聚物的熔融指数为5-13g/10min。
  2. 根据权利要求1所述聚丙烯微发泡材料，其特征在于，包括以下重量份计的组分：聚丙烯53～62份、聚1-丁烯接枝马来酸钠2～3份、乙烯-辛烯无规共聚物5～7份、填料10～30份、润滑剂0.1～0.4份、抗氧剂0.1～0.4份。
  3. 根据权利要求1或2所述聚丙烯微发泡材料，其特征在于，所述填料为滑石粉、碳酸钙、碱式硫酸镁晶须中的至少一种。
  4. 根据权利要求1或2所述聚丙烯微发泡材料，其特征在于，所述润滑剂为硬脂酸盐类。
  5. 根据权利要求1或2所述聚丙烯微发泡材料，其特征在于，所述抗氧剂为受阻酚类和/或亚磷酸酯类。
  6. 权利要求1-5任一项所述聚丙烯微发泡材料的制备方法，其特征在于，包括以下步骤：将各组分混合均匀，熔融挤出造粒，加入发泡剂，挤出发泡，得到聚丙烯微发泡材料。
  7. 根据权利要求6所述聚丙烯微发泡材料的制备方法，其特征在于，所述发泡剂的添加量为1～3wt％。
  8. 权利要求1-5任一项所述聚丙烯微发泡材料在制备抗压缓冲隔热材料中的应用。
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