WO2020119472A1 - 一种聚丙烯复合材料及其制备方法 - Google Patents

一种聚丙烯复合材料及其制备方法 Download PDF

Info

Publication number
WO2020119472A1
WO2020119472A1 PCT/CN2019/121820 CN2019121820W WO2020119472A1 WO 2020119472 A1 WO2020119472 A1 WO 2020119472A1 CN 2019121820 W CN2019121820 W CN 2019121820W WO 2020119472 A1 WO2020119472 A1 WO 2020119472A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon black
composite material
polypropylene composite
polypropylene
weight
Prior art date
Application number
PCT/CN2019/121820
Other languages
English (en)
French (fr)
Inventor
卢朝亮
黄险波
叶南飚
苏娟霞
彭莉
杨波
罗忠富
Original Assignee
金发科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 金发科技股份有限公司 filed Critical 金发科技股份有限公司
Publication of WO2020119472A1 publication Critical patent/WO2020119472A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to a polypropylene composite material and a preparation method thereof, which belong to the technical field of polymer materials.
  • Chinese patent CN102604209A uses a nucleating agent as a modifying component.
  • the nucleating agent can refine the polypropylene spherulite, make the crystal more uniform, regular, and increase the degree of crystallinity, which is effective Reduce the lattice defects of the matrix, prevent oxygen from freely diffusing from the surface of the sample to the inside, thereby improving the resistance to thermal oxygen aging;
  • CN102827422A makes the ⁇ crystal form of polypropylene by adding ⁇ nucleating agent, and the addition of grafting aid improves
  • the interfacial compatibility of polypropylene and inorganic fillers prevents the free diffusion of oxygen from the surface of the sample to the inside, and after processing and molding, when polypropylene products are used at higher temperatures for a long time, the polypropylene will degrade with free radicals
  • the double bond on the grafting aid reacts to stop the degradation reaction, which plays a role in improving the material's resistance to thermal oxygen aging
  • the prepared polypropylene material does not have a color, and most of the interior and exterior materials we use in automobiles and functional parts around the engine are mainly black.
  • Practice has shown that the addition of the colorant carbon black It has a very significant effect on the thermal aging properties of polypropylene.
  • commercial polypropylene products usually have nucleating agent added, and the nucleating agent added in the formulation optimization process generally has its limitations on the improvement of polypropylene crystal form.
  • the compounding of antioxidants through the method of intercalating agent has certain operational complexity in operation. Therefore, there is still a need in the art to develop a thermal oxidation-resistant aging modification method that is simple to prepare and can be effectively applied to black polypropylene products. This method should be suitable for other applications such as automotive interior and exterior trims or home appliances.
  • the object of the present invention is to overcome the deficiencies of the prior art and provide a black polypropylene composition with excellent resistance to thermal oxygen aging.
  • a polypropylene composite material comprising the following components: polypropylene 40-98 parts by weight, toughening agent 0-25 parts by weight, filler 0-30 parts by weight , 0.5-3 parts by weight of non-oxidative modified carbon black treated with surface modifiers and additives;
  • the specific surface area of the non-oxidizing modified carbon black is not more than 170m 2 /g, the oil absorption value is not less than 70mL/100g, and the high-temperature volatile matter of the non-oxidizing modified carbon black is less than 0.3%;
  • the auxiliary agent includes 0.1-0.6 parts by weight of antioxidant.
  • the specific surface area and oil absorption value of the non-oxidative modified carbon black belong to the characteristics of carbon black products, and can be tested according to the standards of the carbon black industry.
  • the measurement method of the specific surface area of the non-oxidative modified carbon black is: the nitrogen adsorption method is used for testing, and the specific surface area of the non-oxidative modified carbon black is calculated based on the BET multimolecular layer adsorption theory.
  • the test result represents the The total specific surface area of carbon black.
  • the test method for the oil absorption value of the non-oxidized modified carbon black is to test the minimum amount of dibutyl phthalate required for the voids and surface infiltration filled with carbon black chain branches or fiber structures, also known as DBP oil absorption value.
  • the high-temperature volatile matter of non-oxidizing modified carbon black refers to the weight loss of carbon black tested above 900°C under nitrogen, which can be measured by the following method: using the crucible burning method, adding the dried non-oxidizing modified Carbon black, accurately burned at 950 ⁇ 20°C for 7 minutes, weighed after cooling for 2 minutes, and the mass loss ratio before and after measurement.
  • the present invention selects carbon black with a specific surface area and specific oil absorption value as a raw material through appropriate screening of carbon black, and uses a surface modifier to perform surface treatment on it, so that the carbon black surface can effectively control the polypropylene polymer chain
  • the adsorption reduces the interfacial stress between carbon black and polypropylene.
  • the surface-treated carbon black has better dispersibility, which can prevent the interfacial stress caused by the presence of large-sized agglomerates in the system, and can reduce the effective contact between the carbon black and the antioxidant in the formulation system, thus reducing its antioxidant Oxidation.
  • the present invention can effectively improve the thermal oxygen aging resistance of the black polypropylene composite material by using the treated specific carbon black, and at the same time reduce the amount of antioxidant in the product, reduce the cost and reduce the precipitation of antioxidant risk.
  • the non-oxidatively modified carbon black is 0.8 to 2 parts by weight. Carbon black needs to be added according to the color matching requirements. The amount of carbon black added is too low, and the blackness of polypropylene composite materials is not good. If the amount of carbon black added is too high, the thermal aging resistance of polypropylene composite materials will deteriorate, and the cost will increase. . When the non-oxidative modified carbon black is 0.8 ⁇ 2 parts by weight, the polypropylene composite material has the best anti-oxidative aging effect, the amount of addition continues to increase, and the blackness does not increase much, but the anti-oxidative aging will significantly deteriorate.
  • the preparation method of the non-oxidizing modified carbon black is: mixing the non-oxidizing carbon black and the surface modifier and spray coating to obtain the surface modified Non-oxidative modified carbon black moistened by chemical agents.
  • the non-oxidizing carbon black and the surface modifier are spray coated after being mixed by the mixing device. The spray coating treatment improves the dispersibility of the obtained non-oxidative modified carbon black.
  • the weight ratio of the non-oxidizing carbon black and the surface modifier is 0.5 to 3: 0.2 to 2.
  • the non-oxidizing carbon black is at least one of furnace black, thermal cracking black, and acetylene black.
  • the surface modifier is at least one of a silane coupling agent, a titanate coupling agent, a stearate, and a stearate.
  • the polypropylene is a copolymer polypropylene, the melt flow rate (MFR) of the polypropylene is 1-100g/10min, and the melt flow rate of the polypropylene is 2.16kg weight according to ASTM D1238 And measured at 230 °C temperature;
  • the toughening agent is at least one of polyolefin elastomer (POE), styrene-hydrogenated butadiene block copolymer (SEBS), and EPDM (EPDM);
  • POE polyolefin elastomer
  • SEBS styrene-hydrogenated butadiene block copolymer
  • EPDM EPDM
  • the filler is at least one of talc, calcium carbonate, wollastonite, whiskers and glass fibers;
  • the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; preferably, the antioxidants are composed of primary antioxidants and auxiliary antioxidants, so The primary antioxidant is at least one of antioxidant 1010, antioxidant AO-330, antioxidant 3114, etc., and the auxiliary antioxidant is antioxidant 168, antioxidant PEP-36, etc. At least one.
  • the auxiliary agent is 0.2 to 2 parts. Different additives will have different effects on the performance of the polypropylene composite material. In practical applications, specific additives or combinations of additives and specific amounts of additives can be selected according to the comprehensive properties of the polypropylene composite material required.
  • the auxiliary agent further includes at least one of a light stabilizer and a lubricant; preferably, the light stabilizer is a hindered amine light stabilizer,
  • the lubricant is at least one of silicone-based lubricants, ester-based lubricants, amide-based lubricants, polyethylene-based lubricants, and fatty acid-based lubricants; more preferably, the hindered amine-based light stabilizer is UV- At least one of 3808PP5, LA-402XP, and LA-402AF; the fatty acid lubricant is a stearic acid lubricant.
  • the present invention also provides a method for preparing the above polypropylene composite material, which includes the following steps: the components in the polypropylene composite material are uniformly mixed in parts by weight, and then added to a twin-screw extruder for melt kneading, Extrusion and granulation to obtain the polypropylene composite material; wherein the temperature of melt-kneading is 170-220°C, and the rotation speed of the screw is 350-450 rpm.
  • the beneficial effects of the present invention are: the present invention can effectively reduce the negative impact of carbon black on the thermal aging resistance of polypropylene composite materials by using the treated specific carbon black, and at the same time reduce the antioxidant in the product
  • the dosage of the agent reduces the cost and reduces the risk of antioxidant precipitation.
  • the polypropylene composite material prepared by the invention satisfies the higher requirements of general automobile interiors for thermal oxygen aging, and has the characteristics of stable thermal oxygen aging resistance.
  • the polypropylene composite material of the present invention is colored by carbon black and has a black appearance, and can be used to prepare products such as automotive interior and exterior trim parts and the periphery of the engine that have strict requirements on the material's resistance to thermal oxygen aging.
  • the preparation method of the polypropylene composite material of the invention is simple and easy to implement.
  • melt flow rate (MFR) of polypropylene is measured according to ASTM D1238 using a weight of 2.16 kg and a temperature of 230°C.
  • the materials in the examples that are not specifically explained are all commercially available.
  • POE polyolefin elastomer
  • SEBS styrene-hydrogenated butadiene block copolymer
  • EPDM EPDM
  • the components of the polypropylene composite materials of Examples 1 to 5 are shown in Table 1.
  • the preparation method of the polypropylene composite material of Examples 1 to 5 is as follows: the components of the polypropylene composite material are uniformly mixed in parts by weight, and then added to a twin-screw extruder for melt-kneading and extrusion granulation to obtain The polypropylene composite material; wherein, the temperature of melt-kneading is 170-220° C., and the rotation speed of the screw is 350-450 rpm.
  • the preparation method of the non-oxidative modified carbon black treated with the surface modifier is: mixing the non-oxidative carbon black and the surface modifier and spray coating to obtain a wetted surface modifier Non-oxidative modified carbon black.
  • the weight ratio of non-oxidizing carbon black and surface modifier and their types are shown in Table 2.
  • the method of performance test is: place the sample in a ventilated hot oxygen aging box, set the temperature to 150 °C, ventilation frequency 150 times/hour, observe the surface condition of the sample regularly, when the surface of the sample shows obvious discoloration, bubbles, powder
  • the initial aging time is the time of chemical and cracking.
  • the thermal aging resistance of the material is characterized by recording the initial aging time. The longer the time, the better the thermal aging resistance of the material. The test results are shown in Table 1.
  • the polypropylene composite material of the present invention has excellent resistance to thermal oxygen aging.
  • the choice of carbon black pigment in the polypropylene composite material of the present invention affects the thermal oxidation resistance of the polypropylene composite material.
  • polypropylene composite materials of the following test groups 1 to 3 and control groups 1 to 8 were prepared, and each test group was tested in accordance with the test method for the properties of the polypropylene composite materials of examples 1 to 5 The heat resistance and oxygen aging resistance of the polypropylene composite in the control group.
  • the test group 1 to 3 and the control group 1 to 8 polypropylene composite materials are composed of the following components: copolymerized polypropylene 70 parts by weight, POE (toughening agent) 8 parts by weight, talc (filler) 20 parts by weight, the main resistance 0.2 parts by weight of oxygen agent, 0.2 parts by weight of auxiliary antioxidant, 0.4 parts by weight of light stabilizer and carbon black pigment; wherein, the melt flow rate (MFR) of the copolymerized polypropylene is 1 to 100 g/10 min.
  • MFR melt flow rate
  • the polypropylene composite materials of each test group and control group are the same except for the carbon black pigment used.
  • the test results of carbon black pigments and polypropylene composites in the experimental groups 1 to 3 and the control groups 1 to 8 in polypropylene composite materials are shown in Table 3.
  • the non-oxidizing carbon black is not surface-treated, and the preparation method of the non-oxidizing modified carbon black is: combining the non-oxidizing carbon black and the alkyl silane coupling agent (surface modifier) in accordance with 2:1 After mixing by weight ratio, spray coating is performed to obtain a non-oxidized modified carbon black wetted with an alkylsilane coupling agent.
  • control group 1 is a natural sample, does not contain carbon black, and its thermal oxygen aging resistance can meet the most stringent automotive oxygen product aging resistance requirements at 150°C and 1000h. It can be seen from the control group 2-3 that when carbon black is not surface-treated, the thermal aging resistance of the polypropylene composite material is greatly affected; further comparison between the test group 1-3 and the control group 2-3 can be seen, Surface treatment of carbon black by coupling agent can effectively improve the adverse effect of carbon black on thermal aging resistance of polypropylene composite materials.
  • the proportion of non-oxidatively modified carbon black in the polypropylene composite material of the present invention will affect the blackness and thermal aging resistance of the polypropylene composite material.
  • this effect example prepared the polypropylene composite materials of the following test groups 1 to 5 and the control groups 1 to 4 and tested each test group with the test methods for the properties of the polypropylene composite materials of Examples 1 to 5 The thermal resistance of polypropylene composite in the control group.
  • Table 4 shows the composition and performance test results of the polypropylene composites of the test groups 1 to 5 and the control groups 1 to 4. Among them, the test groups 1 and 2 are the same as the test groups 1 and 2 in the effect example 1.
  • the melt flow rate (MFR) of the copolymerized polypropylene is 1 to 100 g/10 min.
  • the preparation method of the non-oxidized modified carbon black is: the non-oxidized carbon black and the alkyl silane coupling agent (surface (Modifier) mixed in a weight ratio of 2:1 and spray coated to obtain a non-oxidized modified carbon black wetted with an alkylsilane coupling agent.
  • the amount of non-oxidative modified carbon black affects the blackness of polypropylene composite materials and the resistance to thermal oxygen aging.
  • the amount of non-oxidized modified carbon black is too low, the blackness of polypropylene composite material is not good; when the amount of non-oxidized modified carbon black is too high, the thermal aging resistance of polypropylene composite material becomes poor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及一种聚丙烯复合材料及其制备方法，属于高分子材料技术领域。本发明的聚丙烯复合材料包括下述组分：聚丙烯40～98重量份，增韧剂0～25重量份，填料0～30重量份，经表面改性剂处理的非氧化性改性炭黑0.5～3重量份以及助剂；所述非氧化性改性炭黑的比表面积不大于170m 2/g，吸油值不小于70mL/100g，且所述非氧化性改性炭黑的高温挥发份低于0.3％；所述助剂包括0.1～0.6重量份抗氧剂。本发明通过采用经处理的特定炭黑，能有效降低炭黑对于聚丙烯复合材料抗热氧老化性能的负面影响，同时降低产品中抗氧剂的用量，降低成本以及减少抗氧剂析出风险。本发明制得的聚丙烯复合材料满足一般汽车内饰对于热氧老化的更高要求，具有抗热氧老化性能稳定的特点。

Description

一种聚丙烯复合材料及其制备方法 技术领域
本发明涉及一种聚丙烯复合材料及其制备方法，属于高分子材料技术领域。
背景技术
为了改善材料的抗热氧老化性能，中国专利CN102604209A采用成核剂作为改性组分，成核剂可以使聚丙烯球晶细化、使结晶更加均匀化、规整化、结晶度增加，从而有效降低了基体的晶格缺陷，阻止氧气从样品表面向内部自由扩散，从而提高抗热氧老化性能；CN102827422A通过添加β成核剂使聚丙烯形成β晶型，同时接枝助剂的加入提高了聚丙烯与无机填料的界面相容性，阻止了氧气从样品表面向内部自由扩散，并且在加工成型后，聚丙烯制品长期在较高温度下使用时，聚丙烯发生降解生成自由基时会与接枝助剂上的双键发生反应，使降解反应终止，而起到提高材料抗热氧老化的作用；CN103694552A通过插层反应，将受阻酚化合物以弱化学键的形式固定在LDH的层板之间，制备了受阻酚插层层状复合金属氢氧化物(AO-LDH)，与聚丙烯进行混合，防止抗氧剂的迁移，提高聚丙烯材料的抗热氧老化性能。
然而上述专利公开的方法中，所制备的聚丙烯材料都不具有颜色，而我们在汽车上应用的内外饰材料以及发动机周边功能件大部分都以黑色为主，实践表明着色剂炭黑的加入对聚丙烯热氧老化性能有非常显著的影响。其次是商业化的聚丙烯产品通常都已有成核剂的添加，配方优化过程中外加的成核剂一般对聚丙烯晶型的改善有其局限性。再者通过插层剂的方法复合抗氧剂，在操作上具有一定的操作复杂性。因此本领域尚需开发一种制备简单且能有效适用于黑色聚丙烯产品的抗热氧老化改性方法，该方法应适用于汽车内外饰件或家电等其它应用领域。
发明内容
本发明的目的在于克服现有技术的不足之处而提供一种具有优异抗热氧老 化性能的黑色聚丙烯组合物。
为实现上述目的，本发明采取的技术方案为：一种聚丙烯复合材料，其包括下述组分：聚丙烯40～98重量份，增韧剂0～25重量份，填料0～30重量份，经表面改性剂处理的非氧化性改性炭黑0.5～3重量份以及助剂；
所述非氧化性改性炭黑的比表面积不大于170m 2/g，吸油值不小于70mL/100g，且所述非氧化性改性炭黑的高温挥发份低于0.3％；
所述助剂包括0.1-0.6重量份抗氧剂。
上述聚丙烯复合材料中，非氧化性改性炭黑的比表面积和吸油值属于炭黑产品的特性，根据炭黑工业的标准进行测试即可。具体地，非氧化性改性炭黑的比表面积的测定方法为：采用氮吸附法进行测试，并基于BET多分子层吸附理论进行计算非氧化性改性炭黑的比表面积，测试结果代表了炭黑的总比表面积。非氧化性改性炭黑的吸油值的测试方法为：测试充满炭黑链枝或者纤维结构的空隙及表面浸润所需的最低邻苯二甲酸二丁酯的量，也称DBP吸油值。非氧化性改性炭黑的高温挥发份指的是氮气条件下炭黑在900℃以上测试的重量损失，可采用下述方法进行测定：用坩埚灼烧法，加入干燥过的非氧化性改性炭黑，于950±20℃条件下准确灼烧7min，冷却2min后称重，计量前后的质量损失比例。
本发明通过对炭黑进行适当筛选，选择出特定比表面积和特定吸油值的炭黑作为原料，并采用表面改性剂对其进行表面处理，这样能有效控制炭黑表面对聚丙烯高分子链的吸附，降低了炭黑与聚丙烯间的界面应力。同时，进行过表面处理的炭黑，分散性更佳，可防止体系中存在大尺寸团聚体产生界面应力，并能降低炭黑与配方体系中抗氧剂的有效接触，故而降低其对抗氧剂的氧化作用。综合这两个方面，本发明通过采用经处理的特定炭黑，能有效提高黑色聚丙烯复合材料的抗热氧老化性能，同时降低产品中抗氧剂的用量，降低成本以及减少抗氧剂析出风险。
作为本发明所述聚丙烯复合材料的优选实施方式，所述非氧化性改性炭黑为0.8～2重量份。炭黑需按配色的需求添加，炭黑添加量过低，聚丙烯复合材料的黑度不佳，炭黑添加量过高会导致聚丙烯复合材料的抗热老化性能变差，且 提高了成本。当非氧化性改性炭黑为0.8～2重量份时，聚丙烯复合材料的抗热氧老化效果最好，添加量继续提升，黑度提高不多，但是抗热氧老化会显著变差。
作为本发明所述聚丙烯复合材料的优选实施方式，所述非氧化性改性炭黑的制备方法为：将非氧化性炭黑和表面改性剂混合后进行喷雾包覆，得到被表面改性剂润湿的非氧化性改性炭黑。优选地，所述非氧化性炭黑和表面改性剂在混合设备混合后进行喷雾包覆。通过喷雾包覆处理，所得非氧化性改性炭黑的分散性分散性得到提高。
作为本发明所述聚丙烯复合材料的优选实施方式，所述非氧化性炭黑和表面改性剂的重量比为0.5～3：0.2～2。
作为本发明所述聚丙烯复合材料的优选实施方式，所述非氧化性炭黑为炉法炭黑、热裂解法炭黑、乙炔炭黑中的至少一种。
作为本发明所述聚丙烯复合材料的优选实施方式，所述表面改性剂为硅烷类偶联剂、钛酸酯偶联剂、硬脂酸盐、硬脂酸酯中的至少一种。
作为本发明所述聚丙烯复合材料的优选实施方式，如下(a)～(d)中的至少一项：
(a)所述聚丙烯为共聚聚丙烯，所述聚丙烯的熔体质量流动速率(MFR)为1～100g/10min，所述聚丙烯的熔体质量流动速率是根据ASTM D1238使用2.16kg重量并在230℃的温度测量；
(b)所述增韧剂为聚烯烃弹性体(POE)、苯乙烯-氢化丁二烯嵌段共聚物(SEBS)、三元乙丙橡胶(EPDM)中的至少一种；
(c)所述填料为滑石粉、碳酸钙、硅灰石、晶须和玻璃纤维中的至少一种；
(d)所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种；优选地，所述抗氧剂由主抗氧剂和辅助抗氧剂组成，所述主抗氧剂为抗氧剂1010、抗氧剂AO-330、抗氧剂3114等中的至少一种，所述辅助抗氧剂为抗氧剂168、抗氧剂PEP-36等中的至少一种。
作为本发明所述聚丙烯复合材料的优选实施方式，所述助剂为0.2～2份。不同助剂会给聚丙烯复合材料的性能产生不同的影响，实际应用中，可根据所需 聚丙烯复合材料的综合性能选择具体的助剂或助剂组合，以及具体的助剂用量。
作为本发明所述聚丙烯复合材料的优选实施方式，所述助剂还包括光稳定剂、润滑剂中的至少一种；优选地，所述光稳定剂为受阻胺类光稳定剂，所述润滑剂为硅酮类润滑剂、酯类润滑剂、酰胺类润滑剂、聚乙烯类润滑剂、脂肪酸类润滑剂中的至少一种；更优选地，所述受阻胺类光稳定剂为UV-3808PP5、LA-402XP、LA-402AF中的至少一种；所述脂肪酸类润滑剂为硬脂酸类润滑剂。
另外，本发明还提供了上述聚丙烯复合材料的制备方法，其包括以下步骤：将聚丙烯复合材料中的各组分按重量份混合均匀后加入双螺杆挤出机中，进行熔融混炼、挤出造粒，得到所述聚丙烯复合材料；其中，熔融混炼的温度为170～220℃，螺杆的转速为350～450转/分。
与现有技术相比，本发明的有益效果为：本发明通过采用经处理的特定炭黑，能有效降低炭黑对于聚丙烯复合材料抗热氧老化性能的负面影响，同时降低产品中抗氧剂的用量，降低成本以及减少抗氧剂析出风险。本发明制得的聚丙烯复合材料满足一般汽车内饰对于热氧老化的更高要求，具有抗热氧老化性能稳定的特点。本发明的聚丙烯复合材料通过炭黑着色，具有黑色外观，可用于制备汽车内外饰件以及发动机周边等对材料抗热氧老化性能有严格要求的产品。
此外，本发明聚丙烯复合材料的制备方法简单便于实行。
具体实施方式
为更好地说明本发明的目的、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。
下述实施例中，聚丙烯的熔体质量流动速率(MFR)是根据ASTM D1238使用2.16kg重量并在230℃的温度测量。实施例中未作特别说明的物质，均从市场上购买得到。
下述实施例中，POE表示聚烯烃弹性体、SEBS表示苯乙烯-氢化丁二烯嵌段共聚物、EPDM表示三元乙丙橡胶。
实施例1～5
实施例1～5的聚丙烯复合材料的组分如表1所示。实施例1～5的聚丙烯复合材料的制备方法为：将聚丙烯复合材料中的各组分按重量份混合均匀后加入双螺杆挤出机中，进行熔融混炼、挤出造粒，得到所述聚丙烯复合材料；其中，熔融混炼的温度为170～220℃，螺杆的转速为350～450转/分。
各实施例中，经表面改性剂处理的非氧化性改性炭黑的制备方法为：将非氧化性炭黑和表面改性剂混合后进行喷雾包覆，得到被表面改性剂润湿的非氧化性改性炭黑。制备时，非氧化性炭黑和表面改性剂的重量比以及它们的类型如表2所示。
制得实施例1～5的聚丙烯复合材料后，将其注塑成100mm*100mm*2mm样片，进行性能测试。性能测试的方法为：将样片置于换气式热氧老化箱，设置温度为150℃，换气频率150次/小时，定时观测样片的表面状况，当样片表面出现明显的变色、气泡、粉化、开裂时为其开始老化时间，通过记录开始老化时间对材料的抗热氧老化性能进行表征，时间越长说明材料的抗热氧老化性能越好。测试结果如表1所示。
表1
Figure PCTCN2019121820-appb-000001
Figure PCTCN2019121820-appb-000002
由表1可见，本发明的聚丙烯复合材料具有优异的抗热氧老化性能。
表2
Figure PCTCN2019121820-appb-000003
Figure PCTCN2019121820-appb-000004
效果例1
本发明聚丙烯复合材料中炭黑颜料的选择影响聚丙烯复合材料的抗热氧老化性能。为了考察该影响，本效果例制备了下述试验组1～3以及对照组1～8的聚丙烯复合材料，并按照实施例1～5聚丙烯复合材料性能的测试方法测试了各试验组与对照组聚丙烯复合材料的抗热氧老化性能。
试验组1～3以及对照组1～8聚丙烯复合材料由下述组分组成：共聚聚丙烯70重量份，POE(增韧剂)8重量份，滑石粉(填料)20重量份，主抗氧剂0.2重量份，辅助抗氧剂0.2重量份，光稳定剂0.4重量份以及炭黑颜料；其中，共聚聚丙烯的熔体质量流动速率(MFR)为1～100g/10min。
各试验组以及对照组聚丙烯复合材料除所采用的炭黑颜料不同之外，其他均相同。试验组1～3以及对照组1～8聚丙烯复合材料中的炭黑颜料以及聚丙烯复合材料的抗热氧老化性能测试结果如表3所示。表3中，非氧化性炭黑未经表面处理，非氧化性改性炭黑的制备方法为：将非氧化性炭黑和烷基硅烷偶联剂(表面改性剂)按照2：1的重量比混合后进行喷雾包覆，得到被烷基硅烷偶联剂润湿的非氧化性改性炭黑。
表3
Figure PCTCN2019121820-appb-000005
Figure PCTCN2019121820-appb-000006
表3中，高温挥发份“-”表示无高温挥发物。
上述表3中，对照组1为本色样品，不含有炭黑，其抗热氧老化性能可以满足汽车产品最为严格的150℃、1000h的抗热氧老化要求。通过对照组2-3可以看出，当炭黑没有进行表面处理，聚丙烯复合材料的抗热氧老化性受到较大影响；进一步比较试验组1-3与对照组2-3可以看出，通过偶联剂对炭黑进行表面处理，可以有效改善炭黑对聚丙烯复合材料抗热氧老化性能的不利影响。
比较试验组1-3与对照组4-8可以看出，当炭黑的比表面积/吸油值/高温挥发份不在本发明所述范围内时，聚丙烯复合材料的抗热氧老化性受到较大的影响；当炭黑经过筛选处于本发明范围内时，炭黑对对聚丙烯组合物的热氧老化性能的影响小于选用未经过优化筛选但经过表面处理的炭黑。
综上，通过筛选炭黑和对炭黑进行表面处理，能在很大程度上减弱炭黑对聚丙烯复合材料抗热氧老化性能的影响，得到抗热氧老化效果优秀的聚丙烯复合材料。
效果例2
本发明聚丙烯复合材料中非氧化性改性炭黑的比例会影响聚丙烯复合材料的黑度和抗热氧老化性能。为了考察该影响，本效果例制备了下述试验组1～5以及对照组1～4的聚丙烯复合材料，并按照实施例1～5聚丙烯复合材料性能的测试方法测试了各试验组与对照组聚丙烯复合材料的抗热氧化性能。试验组1～5 以及对照组1～4的聚丙烯复合材的组成以及性能测试结果如表4所示。其中，试验组1和2同效果例1中的试验组1和2。
表4
Figure PCTCN2019121820-appb-000007
表4中，高温挥发份“-”表示无高温挥发物。
表4中，共聚聚丙烯的熔体质量流动速率(MFR)为1～100g/10min，非氧化性改性炭黑的制备方法为：将非氧化性炭黑和烷基硅烷偶联剂(表面改性剂)按照2：1的重量比混合后进行喷雾包覆，得到被烷基硅烷偶联剂润湿的非氧化性改性炭黑。
由表4可见，非氧化性改性炭黑的用量影响聚丙烯复合材料的黑度以及抗热氧老化性能。当非氧化性改性炭黑的用量过低，聚丙烯复合材料的黑度不佳；当非氧化性改性炭黑的用量过高，聚丙烯复合材料的抗热老化性能变差。对于应用于汽车发动机周边等对黑度要求不高，但热老化要求高的产品，可以采用低于0.8重量份的炭黑；而当对颜色有需求的产品，当非氧化性改性炭黑为0.8～2重量份时，聚丙烯复合材料的黑度和抗热氧老化效果均较好。
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 (10)

  1. 一种聚丙烯复合材料，其特征在于，包括下述组分：聚丙烯40～98重量份，增韧剂0～25重量份，填料0～30重量份，经表面改性剂处理的非氧化性改性炭黑0.5～3重量份以及助剂；
    所述非氧化性改性炭黑的比表面积不大于170m 2/g，吸油值不小于70mL/100g，且所述非氧化性改性炭黑的高温挥发份低于0.3％；
    所述助剂包括0.1-0.6重量份抗氧剂。
  2. 如权利要求1所述的聚丙烯复合材料，其特征在于，所述非氧化性改性炭黑为0.8～2重量份。
  3. 如权利要求1或2所述的聚丙烯复合材料，其特征在于，所述非氧化性改性炭黑的制备方法为：将非氧化性炭黑和表面改性剂混合后进行喷雾包覆，得到被表面改性剂润湿的非氧化性改性炭黑。
  4. 如权利要求3所述的聚丙烯复合材料，其特征在于，所述非氧化性炭黑和表面改性剂的重量比为0.5～3：0.2～2。
  5. 如权利要求3所述的聚丙烯复合材料，其特征在于，所述非氧化性炭黑为炉法炭黑、热裂解法炭黑、乙炔炭黑中的至少一种。
  6. 如权利要求1所述的聚丙烯复合材料，其特征在于，所述表面改性剂为硅烷类偶联剂、钛酸酯偶联剂、硬脂酸盐、硬脂酸酯中的至少一种。
  7. 如权利要求1所述的聚丙烯复合材料，其特征在于，如下(a)～(d)中的至少一项：
    (a)所述聚丙烯为共聚聚丙烯，所述聚丙烯的熔体质量流动速率为1～100g/10min，所述聚丙烯的熔体质量流动速率是根据ASTM D1238使用2.16kg重量并在230℃的温度测量；
    (b)所述增韧剂为聚烯烃弹性体、苯乙烯-氢化丁二烯嵌段共聚物、三元乙丙橡胶中的至少一种；
    (c)所述填料为滑石粉、碳酸钙、硅灰石、晶须和玻璃纤维中的至少一种；
    (d)所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种；优选地，所述抗氧剂由主抗氧剂和辅助抗氧剂组成，所述主抗氧剂为抗氧剂1010、抗氧剂AO-330、抗氧剂3114中的至少一种，所述辅助抗氧剂为抗氧剂168、抗氧剂PEP-36中的至少一种。
  8. 如权利要求1所述的聚丙烯复合材料，其特征在于，所述助剂为0.2～2份。
  9. 如权利要求1或8所述的聚丙烯复合材料，其特征在于，所述助剂还包括光稳定剂、润滑剂中的至少一种；优选地，所述光稳定剂为受阻胺类光稳定剂，所述润滑剂为硅酮类润滑剂、酯类润滑剂、酰胺类润滑剂、聚乙烯类润滑剂、脂肪酸类润滑剂中的至少一种。
  10. 如权利要求1～9任一项所述聚丙烯复合材料的制备方法，其特征在于，包括以下步骤：将聚丙烯复合材料中的各组分按重量份混合均匀后加入双螺杆挤出机中，进行熔融混炼、挤出造粒，得到所述聚丙烯复合材料；其中，熔融混炼的温度为170～220℃，螺杆的转速为350～450转/分。
PCT/CN2019/121820 2018-12-13 2019-11-29 一种聚丙烯复合材料及其制备方法 WO2020119472A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811527135.8 2018-12-13
CN201811527135.8A CN109627601B (zh) 2018-12-13 2018-12-13 一种聚丙烯复合材料及其制备方法

Publications (1)

Publication Number Publication Date
WO2020119472A1 true WO2020119472A1 (zh) 2020-06-18

Family

ID=66073717

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/121820 WO2020119472A1 (zh) 2018-12-13 2019-11-29 一种聚丙烯复合材料及其制备方法

Country Status (2)

Country Link
CN (1) CN109627601B (zh)
WO (1) WO2020119472A1 (zh)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995811A (zh) * 2020-08-17 2020-11-27 新奥石墨烯技术有限公司 石墨烯改性超高分子量聚乙烯及其制备方法
CN112831124A (zh) * 2021-01-25 2021-05-25 青岛海尔新材料研发有限公司 一种汽车水室用可视化耐高温耐水解的长玻纤增强聚丙烯复合材料
CN113024950A (zh) * 2021-03-15 2021-06-25 俞杨林 一种增强增韧聚丙烯塑料及其制备方法
CN113512210A (zh) * 2021-06-01 2021-10-19 诺垦(上海)新材料科技有限公司 一种用于发泡聚苯乙烯的增强母粒及其制备方法
CN113980386A (zh) * 2021-10-29 2022-01-28 金发科技股份有限公司 一种HDPE-g-GMA改性的聚丙烯复合材料及其制备方法和应用
CN114000214A (zh) * 2020-12-30 2022-02-01 江苏青昀新材料科技有限公司 一种改良型闪蒸聚乙烯复合材料
CN114561068A (zh) * 2022-03-04 2022-05-31 江苏金发科技新材料有限公司 一种黑色增强聚丙烯组合物及其制备方法和应用
CN114716763A (zh) * 2022-03-23 2022-07-08 华润化学材料科技股份有限公司 一种耐老化导电聚丙烯功能材料及其制备方法
CN114773733A (zh) * 2022-03-30 2022-07-22 山东祥龙新材料股份有限公司 一种高刚高韧改性聚丙烯复合材料及其制备方法
CN114835927A (zh) * 2022-06-13 2022-08-02 昆山禾振瑞新复合材料有限公司 消除表面麻点的钢琴黑高冲击聚丙烯材料用炭黑母粒及其制备方法
CN114921012A (zh) * 2022-05-18 2022-08-19 深圳市富恒新材料股份有限公司 一种香味型可镭雕软触感珠宝盒复合材料及其制备方法
CN115181392A (zh) * 2022-07-27 2022-10-14 上海金山锦湖日丽塑料有限公司 一种耐湿热老化低析出的金属免喷涂abs材料及其制备方法
CN115433410A (zh) * 2022-08-10 2022-12-06 山东寿光鲁清石化有限公司 一种抗菌聚丙烯材料及其制备方法
CN117567810A (zh) * 2024-01-16 2024-02-20 新疆独山子石油化工有限公司 一种多功能型茂金属聚乙烯及其复配添加剂和制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109627601B (zh) * 2018-12-13 2022-02-01 金发科技股份有限公司 一种聚丙烯复合材料及其制备方法
CN113583341B (zh) * 2021-07-28 2023-03-31 金发科技股份有限公司 一种高蓝相高耐热聚丙烯组合物及其制备方法和应用
CN114182383B (zh) * 2021-12-09 2023-11-21 西南石油大学 一种适用于熔喷非织造布的聚丙烯专用料及其制备方法
CN114479271B (zh) * 2022-01-19 2023-10-31 金发科技股份有限公司 一种耐热氧老化聚丙烯组合物及其制备方法和应用
CN114656717A (zh) * 2022-01-21 2022-06-24 金发科技股份有限公司 一种耐候聚丙烯组合物及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003044096A1 (fr) * 2001-11-20 2003-05-30 The Yokohama Rubber Co., Ltd. Noir de carbone traite en surface et composition de caoutchouc contenant ce noir de carbone
CN102010545A (zh) * 2010-10-28 2011-04-13 金发科技股份有限公司 一种抗热氧老化黑色填充聚丙烯复合材料及其制备方法
CN102827422A (zh) * 2012-09-06 2012-12-19 金发科技股份有限公司 一种长期耐热氧老化聚丙烯复合物及其制备方法
CN103467855A (zh) * 2013-09-27 2013-12-25 天津金发新材料有限公司 一种黑色填充聚丙烯复合材料及其制备方法和应用
CN103467856A (zh) * 2013-09-27 2013-12-25 天津金发新材料有限公司 一种黑色玻纤增强聚丙烯复合材料及其制备方法和应用
CN109627601A (zh) * 2018-12-13 2019-04-16 金发科技股份有限公司 一种聚丙烯复合材料及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9207736D0 (en) * 1992-04-08 1992-05-27 Exxon Chemical Patents Inc Ethlene elastomer compounds having good processability and ageing properties
KR100333410B1 (ko) * 2000-05-23 2002-04-25 조충환 트럭버스용 타이어 트레드의 고무 조성물
WO2003074603A1 (en) * 2002-03-01 2003-09-12 Dow Global Technologies Inc. Dimensionally-stable propylene polymer foam with improved thermal aging.
US7166677B2 (en) * 2004-03-19 2007-01-23 Mitsui Chemicals, Inc. Polypropylene resin compositions
CN102030924B (zh) * 2009-09-24 2013-06-26 住友橡胶工业株式会社 轮胎用橡胶组合物以及充气轮胎
CN102604209B (zh) * 2012-02-20 2014-06-18 金发科技股份有限公司 一种耐热氧老化聚丙烯复合物
CN103694552B (zh) * 2012-09-28 2016-02-10 中国石油天然气股份有限公司 一种耐热氧老化聚丙烯组合物及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003044096A1 (fr) * 2001-11-20 2003-05-30 The Yokohama Rubber Co., Ltd. Noir de carbone traite en surface et composition de caoutchouc contenant ce noir de carbone
CN102010545A (zh) * 2010-10-28 2011-04-13 金发科技股份有限公司 一种抗热氧老化黑色填充聚丙烯复合材料及其制备方法
CN102827422A (zh) * 2012-09-06 2012-12-19 金发科技股份有限公司 一种长期耐热氧老化聚丙烯复合物及其制备方法
CN103467855A (zh) * 2013-09-27 2013-12-25 天津金发新材料有限公司 一种黑色填充聚丙烯复合材料及其制备方法和应用
CN103467856A (zh) * 2013-09-27 2013-12-25 天津金发新材料有限公司 一种黑色玻纤增强聚丙烯复合材料及其制备方法和应用
CN109627601A (zh) * 2018-12-13 2019-04-16 金发科技股份有限公司 一种聚丙烯复合材料及其制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
A.R HORROCKS ET AL: "The influence of carbon black on properties of orientated polypropylene 2. Thermal and photodegradation", POLYMER DEGRADATION AND STABILITY, vol. 65, no. 1, 1 July 1999 (1999-07-01), pages 25 - 36, XP085629667, ISSN: 0141-3910, DOI: 10.1016/S0141-3910(98)00213-4 *
J MWILA ET AL: "Effect of carbon black on the oxidation of polyolefins-An overview", POLYMER DEGRADATION AND STABILITY, vol. 44, no. 3, 1 January 1994 (1994-01-01), pages 351 - 356, XP024348674, ISSN: 0141-3910, DOI: 10.1016/0141-3910(94)90094-9 *
WENXIAO LI ET AL: "Research Progress of Oxidative Modification of Carbon Black", DYESTUFFS AND COLORATION, vol. 54, no. 4, 28 August 2017 (2017-08-28), pages 13 - 17, XP009521510, ISSN: 1672-1179 *
YUZHONG LI: "Main properties of various carbon blacks", RUBBER MATERIALS AND MOLDING TECHNOLOGY, 28 February 1989 (1989-02-28), ISBN: 7-5612-0126-5 *
ZONGZHI XIAO: "Effect of Carbon Black on Thermal and Photooxidation of Polyethylene", SYNTHETIC MATERIALS AGING AND APPLICATION, no. 3, 1 October 1983 (1983-10-01), pages 1 - 7, XP009521509, ISSN: 1671-5381, DOI: 10.16584/j.cnki.issn1671-5381.1983.03.001 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995811A (zh) * 2020-08-17 2020-11-27 新奥石墨烯技术有限公司 石墨烯改性超高分子量聚乙烯及其制备方法
CN111995811B (zh) * 2020-08-17 2024-02-06 新奥集团股份有限公司 石墨烯改性超高分子量聚乙烯及其制备方法
CN114000214A (zh) * 2020-12-30 2022-02-01 江苏青昀新材料科技有限公司 一种改良型闪蒸聚乙烯复合材料
CN112831124A (zh) * 2021-01-25 2021-05-25 青岛海尔新材料研发有限公司 一种汽车水室用可视化耐高温耐水解的长玻纤增强聚丙烯复合材料
CN113024950B (zh) * 2021-03-15 2023-05-26 永清县铭达工贸有限公司 一种增强增韧聚丙烯塑料及其制备方法
CN113024950A (zh) * 2021-03-15 2021-06-25 俞杨林 一种增强增韧聚丙烯塑料及其制备方法
CN113512210A (zh) * 2021-06-01 2021-10-19 诺垦(上海)新材料科技有限公司 一种用于发泡聚苯乙烯的增强母粒及其制备方法
CN113980386A (zh) * 2021-10-29 2022-01-28 金发科技股份有限公司 一种HDPE-g-GMA改性的聚丙烯复合材料及其制备方法和应用
CN114561068A (zh) * 2022-03-04 2022-05-31 江苏金发科技新材料有限公司 一种黑色增强聚丙烯组合物及其制备方法和应用
CN114561068B (zh) * 2022-03-04 2023-10-31 江苏金发科技新材料有限公司 一种黑色增强聚丙烯组合物及其制备方法和应用
CN114716763A (zh) * 2022-03-23 2022-07-08 华润化学材料科技股份有限公司 一种耐老化导电聚丙烯功能材料及其制备方法
CN114773733A (zh) * 2022-03-30 2022-07-22 山东祥龙新材料股份有限公司 一种高刚高韧改性聚丙烯复合材料及其制备方法
CN114773733B (zh) * 2022-03-30 2024-02-27 山东祥龙新材料股份有限公司 一种高刚高韧改性聚丙烯复合材料及其制备方法
CN114921012A (zh) * 2022-05-18 2022-08-19 深圳市富恒新材料股份有限公司 一种香味型可镭雕软触感珠宝盒复合材料及其制备方法
CN114835927A (zh) * 2022-06-13 2022-08-02 昆山禾振瑞新复合材料有限公司 消除表面麻点的钢琴黑高冲击聚丙烯材料用炭黑母粒及其制备方法
CN115181392A (zh) * 2022-07-27 2022-10-14 上海金山锦湖日丽塑料有限公司 一种耐湿热老化低析出的金属免喷涂abs材料及其制备方法
CN115181392B (zh) * 2022-07-27 2024-05-03 上海金山锦湖日丽塑料有限公司 一种耐湿热老化低析出的金属免喷涂abs材料及其制备方法
CN115433410A (zh) * 2022-08-10 2022-12-06 山东寿光鲁清石化有限公司 一种抗菌聚丙烯材料及其制备方法
CN117567810A (zh) * 2024-01-16 2024-02-20 新疆独山子石油化工有限公司 一种多功能型茂金属聚乙烯及其复配添加剂和制备方法

Also Published As

Publication number Publication date
CN109627601B (zh) 2022-02-01
CN109627601A (zh) 2019-04-16

Similar Documents

Publication Publication Date Title
WO2020119472A1 (zh) 一种聚丙烯复合材料及其制备方法
CN111004433A (zh) 一种光伏电缆用辐照交联低烟无卤护套材料及其制备方法
CN108623894B (zh) 一种硅烷自交联无卤阻燃材料及其制备方法和应用
CN103890865A (zh) 电线成形体的制造方法
CN112778617A (zh) 一种热塑性低烟无卤聚烯烃电缆料及其制备方法和应用
CN106674768A (zh) 一种三元乙丙橡胶低烟无卤阻燃软胶料
JP3571780B2 (ja) 成形用ポリプロピレン樹脂コンパウンド
WO2021129218A1 (zh) 辐照交联cpe电缆材料及其制备方法和应用
CN112778741A (zh) 一种阻燃聚碳酸酯组合物及其制备方法
CN102432951A (zh) 一种改性三元乙丙胶
CN108530758A (zh) 一种具有长氧化诱导时间的耐热氧化聚丙烯复合材料及其制备方法
JP4953421B2 (ja) 複合水酸化マグネシウム粒子の製造方法
DE112010000865T5 (de) Flammhemmende thermoplastische Vulkanisate
CN111777821B (zh) 一种聚4-甲基-1-戊烯/硅橡胶热塑性弹性体及其制备、应用
US3651176A (en) Method for preparing adhesion-improved ethylene-propylene rubber composition
CN108329647A (zh) 低内应力、高抗冲abs组合物及其制备方法和应用
CN114479271B (zh) 一种耐热氧老化聚丙烯组合物及其制备方法和应用
CN103804859B (zh) 一种高光低挥发聚对苯二甲酸丁二醇酯组合物及其制备方法和应用
CN109705411A (zh) 一种阻燃橡胶母粒
CN106479035B (zh) 一种阻燃耐冲击的聚丙烯复合材料及其制备方法
CN112521675B (zh) 一种绝缘耐寒电缆材料及其制备方法和应用
KR20090042631A (ko) 자동차용 라디에이터 호스 고무 조성물 제조방법
CN115368669B (zh) 一种聚烯烃组合物及其制备方法和应用
CN112280159B (zh) 一种功能型添加剂复合母粒及其制备方法和应用
CN116948386B (zh) 一种阻燃复合电缆材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19896242

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 22/10/2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19896242

Country of ref document: EP

Kind code of ref document: A1