WO2021012888A1 - Thermoplastic cold-resistant pvc material for automobile interior decoration - Google Patents

Thermoplastic cold-resistant pvc material for automobile interior decoration Download PDF

Info

Publication number
WO2021012888A1
WO2021012888A1 PCT/CN2020/098739 CN2020098739W WO2021012888A1 WO 2021012888 A1 WO2021012888 A1 WO 2021012888A1 CN 2020098739 W CN2020098739 W CN 2020098739W WO 2021012888 A1 WO2021012888 A1 WO 2021012888A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
pvc material
cold
automotive interior
Prior art date
Application number
PCT/CN2020/098739
Other languages
French (fr)
Chinese (zh)
Inventor
朱建良
朱伟
曹丽秋
Original Assignee
苏州爱得华塑化有限公司
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 苏州爱得华塑化有限公司 filed Critical 苏州爱得华塑化有限公司
Publication of WO2021012888A1 publication Critical patent/WO2021012888A1/en

Links

Classifications

    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • 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
    • C08J9/06—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 by a chemical blowing agent
    • C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • the present invention generally relates to the field of automotive materials, and more specifically to a thermoplastic cold-resistant automotive interior PVC material.
  • the present invention provides a thermoplastic cold-resistant PVC material for automotive interior decoration.
  • the material still has good toughness when used at low temperatures.
  • thermoplastic cold-resistant automotive interior PVC material which includes the following components: PVC resin powder, phenyl silicone rubber grafted styrene-acrylonitrile (SAN), heat stabilizer, plasticizer Agents, inorganic fillers, foaming agents, lubricants and flame retardants.
  • the proportion of each component is: PVC resin powder 75-90 parts by weight, phenyl silicone rubber grafted styrene-acrylonitrile (SAN) 6-12 parts by weight, and heat stabilizer 8-90 parts by weight. 12 parts by weight, 50-70 parts by weight of plasticizer, 8-15 parts by weight of inorganic filler, 1-2 parts by weight of foaming agent, 2-4 parts by weight of lubricant, and 2-5 parts by weight of flame retardant.
  • SAN phenyl silicone rubber grafted styrene-acrylonitrile
  • phenyl silicone rubber grafted with styrene-acrylonitrile is prepared by seed emulsion polymerization. Specifically prepared by the following methods:
  • Step 1 Prepare seed latex; use deionized water, emulsifier, phenylsiloxane ring, octamethylcyclotetrasiloxane, and tetramethyldisiloxane to pre-emulsify in an emulsifier to prepare monomers
  • emulsifier phenylsiloxane ring, octamethylcyclotetrasiloxane, and tetramethyldisiloxane
  • Step 2 Preparation of grafted styrene-acrylonitrile (SAN) shell layer; continuously adding the shell layer mixture to the rubber core prepared in step 1; the shell layer mixture is composed of deionized water, emulsifier, aryl ethylene The compound and the blend of acrylonitrile and the molecular weight regulator are formed, and the reaction is stirred at the same time to prepare the composite material.
  • SAN grafted styrene-acrylonitrile
  • the plasticizer includes glyceride, isosorbide diester, vegetable oleyl ester, plant-derived polyol ester, adipate, polyadipate, adipate diester, amber One or more of acid ester, sebacic acid ester, and azelaic acid ester.
  • the blowing agent is azodicarbonamide.
  • the heat stabilizer is a calcium zinc heat stabilizer.
  • the inorganic filler includes one or more of talc, quartz, mica, kaolin, wollastonite, montmorillonite, nano calcium carbonate, calcium sulfate, and barium sulfate.
  • the lubricant includes one or more of wax, hydroxyethyl bis fatty acid amide, and ethylene bis oleamide.
  • the flame retardant is antimony trioxide and/or aluminum hydroxide.
  • thermoplastic cold-resistant automotive interior PVC material comprising the following steps:
  • the predetermined temperature is 140-180°C
  • the predetermined time is 2-8 minutes.
  • the phenyl silicone rubber has good low temperature resistance and can be elastic at minus 90°C.
  • the degree of crosslinking of rubber particles is controlled to a low level, which is conducive to its response to external forces, thereby improving the low temperature toughness of PVC resin;
  • SAN styrene-acrylonitrile
  • the phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) was prepared by seed emulsion polymerization.
  • Step 1 Prepare seed latex; use 50-100 parts by weight of deionized water, 1-5 parts by weight of emulsifier, 20-60 parts by weight of phenylsiloxane ring, and 20-50 parts by weight of octamethylcyclotetrasiloxane Parts and 50-80 parts by weight of tetramethyldisiloxane are pre-emulsified in an emulsifier to prepare a pre-emulsified liquid of a monomer blend.
  • the above-mentioned emulsion is added to a mixer, and the ring is opened under the action of an acid catalyst The polymerization reaction is followed by washing with distilled water to neutrality.
  • Step 2 preparation of grafted SAN shell layer; continuously adding shell layer mixture to the rubber core prepared in step 1; the shell layer mixture consists of 24-80 parts by weight deionized water, 0.2-3 parts by weight emulsifier, It is composed of 24-54 parts by weight of a blend of arylethylene compound and acrylonitrile and 0.01-0.1 parts by weight of molecular weight regulator, the reaction temperature is 60°C-90°C, and the stirring speed is 100-500RPM.
  • the PVC material prepared according to the components and methods disclosed in the present invention meets the requirements of various indicators such as hardness, tensile strength, and elongation at break, and the impact brittleness at minus 50 degrees Celsius meets the requirements. Its low temperature performance is significantly improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A thermoplastic cold-resistant PVC material for automobile interior decoration and a preparation method therefor. The material comprises the following components: PVC resin powder, phenyl silicone rubber grafted with styrene-acrylonitrile (SAN), a heat stabilizer, a plasticizer, an inorganic filler, a foaming agent, a lubricant and a flame retardant. By optimizing the composition of the material, the low temperature toughness of the PVC material is improved, and the impact absorption capacity thereof is also improved.

Description

一种热塑性耐寒汽车内饰PVC材料A thermoplastic cold-resistant PVC material for automobile interior decoration 技术领域Technical field
本发明总体涉及汽车材料领域，并且更具体地涉及一种热塑性耐寒汽车内饰PVC材料。The present invention generally relates to the field of automotive materials, and more specifically to a thermoplastic cold-resistant automotive interior PVC material.
背景技术Background technique
汽车内饰材料越来越向着高档化发展，手感柔软，耐折是基本要求，但是，普通PVC材料的柔软性随着温度的变化性能会发生很大改变。在常温下正常使用的材料，在低温状态下，产品会变硬，柔韧性降低，同时使用寿命也降低。通常的做法是添加增塑剂和丁腈橡胶来增加产品的柔韧性，不过在实际使用过程中还是差强人意。因此，仍需研究改善PVC材料低温韧性的方法。Automotive interior materials are becoming more and more high-end development, soft hand feeling and folding resistance are basic requirements, but the flexibility of ordinary PVC materials will change greatly with temperature changes. For materials normally used at room temperature, the product will harden at low temperatures, reduce flexibility, and reduce service life. The usual practice is to add plasticizers and nitrile rubber to increase the flexibility of the product, but it is still not satisfactory in actual use. Therefore, it is still necessary to study methods to improve the low temperature toughness of PVC materials.
发明内容Summary of the invention
针对上述问题，本发明提供一种热塑性耐寒汽车内饰PVC材料。该材料在低温使用时仍具有良好的韧性。In view of the above problems, the present invention provides a thermoplastic cold-resistant PVC material for automotive interior decoration. The material still has good toughness when used at low temperatures.
根据本发明的一方面，提供一种热塑性耐寒汽车内饰PVC材料，该材料包括以下组分：PVC树脂粉、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)、热稳定剂、增塑剂、无机填料、发泡剂、润滑剂和阻燃剂。According to one aspect of the present invention, there is provided a thermoplastic cold-resistant automotive interior PVC material, which includes the following components: PVC resin powder, phenyl silicone rubber grafted styrene-acrylonitrile (SAN), heat stabilizer, plasticizer Agents, inorganic fillers, foaming agents, lubricants and flame retardants.
根据本发明的一个实施例，各组分的配比为：PVC树脂粉75-90重量份、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)6-12重量份、热稳定剂8-12重量份、增塑剂50-70重量份、无机填料8-15重量份、发泡剂1-2重量份、润滑剂2-4重量份、阻燃剂2-5重量份。According to an embodiment of the present invention, the proportion of each component is: PVC resin powder 75-90 parts by weight, phenyl silicone rubber grafted styrene-acrylonitrile (SAN) 6-12 parts by weight, and heat stabilizer 8-90 parts by weight. 12 parts by weight, 50-70 parts by weight of plasticizer, 8-15 parts by weight of inorganic filler, 1-2 parts by weight of foaming agent, 2-4 parts by weight of lubricant, and 2-5 parts by weight of flame retardant.
根据本发明的一个实施例，苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)通 过种子乳液聚合法制得。具体通过以下方法制备：According to an embodiment of the present invention, phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) is prepared by seed emulsion polymerization. Specifically prepared by the following methods:
步骤1，制备种子胶乳；采用去离子水、乳化剂、苯基硅氧烷环体、八甲基环四硅氧烷、四甲基二硅氧烷在乳化机中进行预乳化，制备单体共混物的预乳化液，将上述乳液加入搅拌器中，在酸性催化剂的作用下进行开环聚合反应，之后用蒸馏水洗涤至中性；Step 1. Prepare seed latex; use deionized water, emulsifier, phenylsiloxane ring, octamethylcyclotetrasiloxane, and tetramethyldisiloxane to pre-emulsify in an emulsifier to prepare monomers For the pre-emulsified liquid of the blend, add the above-mentioned emulsion to a stirrer, carry out ring-opening polymerization under the action of an acid catalyst, and then wash with distilled water to neutrality;
步骤2，接枝苯乙烯-丙烯腈(SAN)壳层的制备；向步骤1制备的橡胶核中连续加入壳层混合液；所述壳层混合液由去离子水、乳化剂、芳基乙烯化合物和丙烯腈的共混物、分子量调节剂构成，反应同时搅拌，制备复合材料。Step 2. Preparation of grafted styrene-acrylonitrile (SAN) shell layer; continuously adding the shell layer mixture to the rubber core prepared in step 1; the shell layer mixture is composed of deionized water, emulsifier, aryl ethylene The compound and the blend of acrylonitrile and the molecular weight regulator are formed, and the reaction is stirred at the same time to prepare the composite material.
根据本发明的一个实施例，增塑剂包括甘油酯、异山梨醇二酯、植物油基酯、植物来源的多元醇酯、己二酸酯、聚己二酸酯、己二酸双酯、琥珀酸酯、癸二酸酯、壬二酸酯中的一种或多种。According to an embodiment of the present invention, the plasticizer includes glyceride, isosorbide diester, vegetable oleyl ester, plant-derived polyol ester, adipate, polyadipate, adipate diester, amber One or more of acid ester, sebacic acid ester, and azelaic acid ester.
根据本发明的一个实施例，发泡剂为偶氮二甲酰胺。According to an embodiment of the present invention, the blowing agent is azodicarbonamide.
根据本发明的一个实施例，热稳定剂是钙锌热稳定剂。According to an embodiment of the present invention, the heat stabilizer is a calcium zinc heat stabilizer.
根据本发明的一个实施例，无机填料包括滑石、石英、云母、高岭土、硅灰石、蒙脱石、纳米碳酸钙、硫酸钙、硫酸钡中的一种或多种。According to an embodiment of the present invention, the inorganic filler includes one or more of talc, quartz, mica, kaolin, wollastonite, montmorillonite, nano calcium carbonate, calcium sulfate, and barium sulfate.
根据本发明的一个实施例，润滑剂包括蜡、羟乙基双脂肪酰胺、亚乙基双油酰胺中的一种或多种。According to an embodiment of the present invention, the lubricant includes one or more of wax, hydroxyethyl bis fatty acid amide, and ethylene bis oleamide.
根据本发明的一个实施例，阻燃剂为三氧化二锑和/或氢氧化铝。According to an embodiment of the present invention, the flame retardant is antimony trioxide and/or aluminum hydroxide.
根据本发明的另一方面，提供一种用于制备上述热塑性耐寒汽车内饰PVC材料的方法，该方法包括下列步骤：According to another aspect of the present invention, there is provided a method for preparing the above-mentioned thermoplastic cold-resistant automotive interior PVC material, the method comprising the following steps:
按配比称取PVC树脂粉、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)、热稳定剂、增塑剂、无机填料、发泡剂、润滑剂和阻燃剂；Weigh the PVC resin powder, phenyl silicone rubber grafted styrene-acrylonitrile (SAN), heat stabilizer, plasticizer, inorganic filler, foaming agent, lubricant and flame retardant according to the proportion;
将上述所有物质加入高速混合机上混合，混合预定时间后升温至预定温度塑化混炼；Add all the above-mentioned substances to a high-speed mixer and mix, mix for a predetermined time and then heat up to a predetermined temperature for plasticization and mixing;
然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送 料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
根据本发明的一个实施例，预定温度为140-180℃，预定时间为2-8分钟。According to an embodiment of the present invention, the predetermined temperature is 140-180°C, and the predetermined time is 2-8 minutes.
本发明所公开的热塑性耐寒汽车内饰PVC材料和方法可以获得以下多种有益效果：The thermoplastic cold-resistant automotive interior PVC material and method disclosed in the present invention can obtain the following beneficial effects:
(1)通过对材料的组分进行优化，尤其是采用了苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)，苯基硅橡胶的耐低温性能好，能够在零下90℃具有弹性，将橡胶粒子的交联程度控制的较低，有利于其对外力进行响应，从而改善PVC树脂的低温韧性；(1) By optimizing the composition of the material, especially the use of phenyl silicone rubber grafted with styrene-acrylonitrile (SAN), the phenyl silicone rubber has good low temperature resistance and can be elastic at minus 90°C. The degree of crosslinking of rubber particles is controlled to a low level, which is conducive to its response to external forces, thereby improving the low temperature toughness of PVC resin;
(2)采用苯乙烯-丙烯腈(SAN)提高苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)与PVC基体的界面亲合力，增加界面的相容性。(2) Use styrene-acrylonitrile (SAN) to improve the interface affinity of phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) and the PVC matrix, and increase the compatibility of the interface.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
实施例1Example 1
通过种子乳液聚合法制备苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)。The phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) was prepared by seed emulsion polymerization.
步骤1，制备种子胶乳；采用去离子水50-100重量份、乳化剂1-5重量份、苯基硅氧烷环体20-60重量份、八甲基环四硅氧烷20-50重量份和四甲基二硅氧烷50-80重量份在乳化机中进行预乳化，制备单体共混物的预乳化液，将上述乳液加入搅拌器中，在酸性催化剂的作用下进行开环聚合反应，之后用蒸馏水洗涤至中性。Step 1. Prepare seed latex; use 50-100 parts by weight of deionized water, 1-5 parts by weight of emulsifier, 20-60 parts by weight of phenylsiloxane ring, and 20-50 parts by weight of octamethylcyclotetrasiloxane Parts and 50-80 parts by weight of tetramethyldisiloxane are pre-emulsified in an emulsifier to prepare a pre-emulsified liquid of a monomer blend. The above-mentioned emulsion is added to a mixer, and the ring is opened under the action of an acid catalyst The polymerization reaction is followed by washing with distilled water to neutrality.
步骤2，接枝SAN壳层的制备；向步骤1制备的橡胶核中连续加入壳层混合液；所述壳层混合液由24-80重量份去离子水、0.2-3重量份乳化剂、24-54重量份芳基乙烯化合物和丙烯腈的共混物、0.01-0.1重量份分子量调节剂构成，反应温度为60℃-90℃，搅拌转速为100-500RPM。Step 2, preparation of grafted SAN shell layer; continuously adding shell layer mixture to the rubber core prepared in step 1; the shell layer mixture consists of 24-80 parts by weight deionized water, 0.2-3 parts by weight emulsifier, It is composed of 24-54 parts by weight of a blend of arylethylene compound and acrylonitrile and 0.01-0.1 parts by weight of molecular weight regulator, the reaction temperature is 60°C-90°C, and the stirring speed is 100-500RPM.
实施例2Example 2
首先按以下配比分别称取：PVC树脂粉75重量份、由实施例1制备的苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)6重量份、钙锌热稳定剂8重量份、己二酸酯50重量份、纳米碳酸钙8重量份、偶氮二甲酰胺1重量份、硬脂酸锌2重量份、三氧化二锑2重量份。First, weigh separately according to the following proportions: 75 parts by weight of PVC resin powder, 6 parts by weight of phenyl silicone rubber grafted styrene-acrylonitrile (SAN) prepared in Example 1, 8 parts by weight of calcium zinc heat stabilizer, 50 parts by weight of diacid ester, 8 parts by weight of nano calcium carbonate, 1 part by weight of azodicarbonamide, 2 parts by weight of zinc stearate, and 2 parts by weight of antimony trioxide.
将上述所有物质加入高速混合机上混合，混合2分钟后升温至180℃塑化混炼。Add all the above-mentioned materials to a high-speed mixer to mix, mix for 2 minutes and then heat to 180°C for plasticization and mixing.
然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
实施例3Example 3
首先按以下配比分别称取：PVC树脂粉80重量份、由实施例1制备的苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)8重量份、钙锌热稳定剂9重量份、聚己二酸酯55重量份、石英8重量份、偶氮二甲酰胺1.3重量份、蜡3重量份、三氧化二锑3重量份。First, weigh separately according to the following proportions: 80 parts by weight of PVC resin powder, 8 parts by weight of phenyl silicone rubber grafted styrene-acrylonitrile (SAN) prepared in Example 1, 9 parts by weight of calcium zinc heat stabilizer, and 55 parts by weight of adipate, 8 parts by weight of quartz, 1.3 parts by weight of azodicarbonamide, 3 parts by weight of wax, and 3 parts by weight of antimony trioxide.
将上述所有物质加入高速混合机上混合，混合4分钟后升温至170℃塑化混炼。Add all the above-mentioned materials to a high-speed mixer to mix, mix for 4 minutes and then heat to 170°C for plasticization and mixing.
然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
实施例4Example 4
首先按以下配比分别称取：PVC树脂粉85重量份、由实施例1制备的苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)10重量份、钙锌热稳定剂10重量份、癸二酸酯60重量份、云母12重量份、偶氮二甲酰胺1.5重量份、羟乙基双脂肪酰胺3重量份、氢氧化铝4重量份。First, weigh separately according to the following proportions: 85 parts by weight of PVC resin powder, 10 parts by weight of phenyl silicone rubber grafted styrene-acrylonitrile (SAN) prepared in Example 1, 10 parts by weight of calcium-zinc heat stabilizer, 60 parts by weight of diacid ester, 12 parts by weight of mica, 1.5 parts by weight of azodicarbonamide, 3 parts by weight of hydroxyethyl bisfatty acid amide, and 4 parts by weight of aluminum hydroxide.
将上述所有物质加入高速混合机上混合，混合6分钟后升温至150℃塑化混炼。Add all the above materials to a high-speed mixer to mix, mix for 6 minutes and then heat up to 150°C for plasticization and mixing.
然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送 料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
实施例5Example 5
首先按以下配比分别称取：PVC树脂粉90重量份、由实施例1制备的苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)12重量份、钙锌热稳定剂12重量份、壬二酸酯70重量份、高岭土15重量份、偶氮二甲酰胺2重量份、亚乙基双油酰胺4重量份、三氧化二锑2重量份、氢氧化铝3重量份。First, weigh separately according to the following proportions: 90 parts by weight of PVC resin powder, 12 parts by weight of phenyl silicone rubber grafted styrene-acrylonitrile (SAN) prepared in Example 1, 12 parts by weight of calcium-zinc heat stabilizer, and 70 parts by weight of diacid ester, 15 parts by weight of kaolin, 2 parts by weight of azodicarbonamide, 4 parts by weight of ethylenebisoleamide, 2 parts by weight of antimony trioxide, and 3 parts by weight of aluminum hydroxide.
将上述所有物质加入高速混合机上混合，混合8分钟后升温至140℃塑化混炼。Add all the above-mentioned materials to a high-speed mixer to mix, mix for 8 minutes and then heat up to 140°C for plasticizing and mixing.
然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
上述实施例的性能测试结果如下：The performance test results of the foregoing embodiment are as follows:
Figure PCTCN2020098739-appb-000001
Figure PCTCN2020098739-appb-000001
由上述测试结果可以看出，按照本发明公开的组分和方法制备的PVC材料满足硬度、拉伸强度、及断裂伸长率等各项指标的要求，并且在零下50摄氏度冲击脆性满足要求，其低温性能显著提高。It can be seen from the above test results that the PVC material prepared according to the components and methods disclosed in the present invention meets the requirements of various indicators such as hardness, tensile strength, and elongation at break, and the impact brittleness at minus 50 degrees Celsius meets the requirements. Its low temperature performance is significantly improved.
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本 领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above-mentioned embodiments only express the implementation of the present invention, and the description is relatively specific and detailed, but it should not be understood as a limitation to the patent scope of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention.

Claims (10)

  1. 一种热塑性耐寒汽车内饰PVC材料，其特征在于，所述材料包括以下组分：PVC树脂粉、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)、热稳定剂、增塑剂、无机填料、发泡剂、润滑剂和阻燃剂。A thermoplastic cold-resistant automotive interior PVC material, characterized in that the material comprises the following components: PVC resin powder, phenyl silicone rubber grafted styrene-acrylonitrile (SAN), heat stabilizer, plasticizer, inorganic Fillers, foaming agents, lubricants and flame retardants.
  2. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，各组分的配比为：PVC树脂粉75-90重量份、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)6-12重量份、热稳定剂8-12重量份、增塑剂50-70重量份、无机填料8-15重量份、发泡剂1-2重量份、润滑剂2-4重量份、阻燃剂2-5重量份。The thermoplastic cold-resistant automotive interior PVC material according to claim 1, wherein the proportion of each component is: PVC resin powder 75-90 parts by weight, phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) 6-12 parts by weight, 8-12 parts by weight of heat stabilizer, 50-70 parts by weight of plasticizer, 8-15 parts by weight of inorganic filler, 1-2 parts by weight of foaming agent, 2-4 parts by weight of lubricant, resistance Burning agent 2-5 parts by weight.
  3. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)通过种子乳液聚合法制得。The thermoplastic cold-resistant automotive interior PVC material of claim 1, wherein the phenyl silicone rubber grafted with styrene-acrylonitrile (SAN) is prepared by a seed emulsion polymerization method.
  4. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述增塑剂包括甘油酯、异山梨醇二酯、植物油基酯、植物来源的多元醇酯、己二酸酯、聚己二酸酯，己二酸双酯、琥珀酸酯、癸二酸酯、壬二酸酯中的一种或多种。The thermoplastic cold-resistant automotive interior PVC material of claim 1, wherein the plasticizer includes glyceride, isosorbide diester, vegetable oil-based ester, plant-derived polyol ester, adipate, Polyadipate, one or more of adipate diester, succinate, sebacate, and azelate.
  5. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述热稳定剂是钙锌热稳定剂。The thermoplastic cold-resistant automotive interior PVC material according to claim 1, wherein the heat stabilizer is a calcium-zinc heat stabilizer.
  6. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述无机填料包括滑石、石英、云母、高岭土、硅灰石、蒙脱石、纳米碳酸钙、硫酸钙、硫酸钡中的一种或多种。The thermoplastic cold-resistant automotive interior PVC material of claim 1, wherein the inorganic filler includes talc, quartz, mica, kaolin, wollastonite, montmorillonite, nano calcium carbonate, calcium sulfate, barium sulfate. One or more of.
  7. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述阻燃剂为三氧化二锑和/或氢氧化铝。The thermoplastic cold-resistant automotive interior PVC material according to claim 1, wherein the flame retardant is antimony trioxide and/or aluminum hydroxide.
  8. 根据权利要求1所述的热塑性耐寒汽车内饰PVC材料，其特征在于，所述润滑剂包括蜡、羟乙基双脂肪酰胺、亚乙基双油酰胺中的一种或多种。The thermoplastic cold-resistant automotive interior PVC material according to claim 1, wherein the lubricant includes one or more of wax, hydroxyethyl bis fatty acid amide, and ethylene bis oleamide.
  9. 一种用于制备根据权利要求1-8中任一项所述的热塑性耐寒汽车内饰PVC材料的方法，其特征在于，所述方法包括下列步骤：A method for preparing the thermoplastic cold-resistant automotive interior PVC material according to any one of claims 1-8, wherein the method comprises the following steps:
    按配比称取PVC树脂粉、苯基硅橡胶接枝苯乙烯-丙烯腈(SAN)、热稳定剂、增塑剂、无机填料、发泡剂、润滑剂和阻燃剂；Weigh the PVC resin powder, phenyl silicone rubber grafted styrene-acrylonitrile (SAN), heat stabilizer, plasticizer, inorganic filler, foaming agent, lubricant and flame retardant according to the proportion;
    将上述所有物质加入高速混合机上混合，混合预定时间后升温至预定温度塑化混炼；Add all the above-mentioned substances to a high-speed mixer and mix, mix for a predetermined time and then heat up to a predetermined temperature for plasticization and mixing;
    然后经过双螺杆挤出加工，然后经过单螺杆挤出造粒，旋风分离机送料，振动筛筛分然后包装，即获得耐寒阻燃PVC电缆材料。Then through twin-screw extrusion processing, and then through single-screw extrusion granulation, cyclone separator feeding, vibrating screen sieving and packaging, that is, the cold-resistant flame-retardant PVC cable material is obtained.
  10. 根据权利要求9所述的方法，其特征在于，所述预定温度为140-180℃，所述预定时间为2-8分钟。The method according to claim 9, wherein the predetermined temperature is 140-180°C, and the predetermined time is 2-8 minutes.
PCT/CN2020/098739 2019-07-19 2020-06-29 Thermoplastic cold-resistant pvc material for automobile interior decoration WO2021012888A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910653271.XA CN110256787A (en) 2019-07-19 2019-07-19 A kind of cold-resistant automobile interior decoration PVC material of thermoplasticity
CN201910653271.X 2019-07-19

Publications (1)

Publication Number Publication Date
WO2021012888A1 true WO2021012888A1 (en) 2021-01-28

Family

ID=67927100

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/098739 WO2021012888A1 (en) 2019-07-19 2020-06-29 Thermoplastic cold-resistant pvc material for automobile interior decoration

Country Status (2)

Country Link
CN (1) CN110256787A (en)
WO (1) WO2021012888A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110256787A (en) * 2019-07-19 2019-09-20 苏州爱得华塑化有限公司 A kind of cold-resistant automobile interior decoration PVC material of thermoplasticity

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003238639A (en) * 2002-02-15 2003-08-27 Kanegafuchi Chem Ind Co Ltd Graft copolymer and flame-retardant resin composition containing the same
US20050014897A1 (en) * 2003-04-22 2005-01-20 Alfred Eitel Process and device for the production of elastomer-modified thermoplastics
CN101338059A (en) * 2007-07-03 2009-01-07 广州市波斯塑胶颜料有限公司 PVC modified material and method for preparing same
CN101790550A (en) * 2007-07-13 2010-07-28 三菱丽阳株式会社 Graft copolymer, thermoplastic resin composition, and molded object
CN105732908A (en) * 2014-12-10 2016-07-06 中国石油天然气股份有限公司 A preparing method of a rubber graft copolymer and applications of the rubber graft copolymer
CN109627387A (en) * 2018-12-04 2019-04-16 重庆云天化瀚恩新材料开发有限公司 Acrylate-styrene bipolymer-acrylonitrile core-shell graft copolymer preparation method
CN110256787A (en) * 2019-07-19 2019-09-20 苏州爱得华塑化有限公司 A kind of cold-resistant automobile interior decoration PVC material of thermoplasticity

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003238639A (en) * 2002-02-15 2003-08-27 Kanegafuchi Chem Ind Co Ltd Graft copolymer and flame-retardant resin composition containing the same
US20050014897A1 (en) * 2003-04-22 2005-01-20 Alfred Eitel Process and device for the production of elastomer-modified thermoplastics
CN101338059A (en) * 2007-07-03 2009-01-07 广州市波斯塑胶颜料有限公司 PVC modified material and method for preparing same
CN101790550A (en) * 2007-07-13 2010-07-28 三菱丽阳株式会社 Graft copolymer, thermoplastic resin composition, and molded object
CN105732908A (en) * 2014-12-10 2016-07-06 中国石油天然气股份有限公司 A preparing method of a rubber graft copolymer and applications of the rubber graft copolymer
CN109627387A (en) * 2018-12-04 2019-04-16 重庆云天化瀚恩新材料开发有限公司 Acrylate-styrene bipolymer-acrylonitrile core-shell graft copolymer preparation method
CN110256787A (en) * 2019-07-19 2019-09-20 苏州爱得华塑化有限公司 A kind of cold-resistant automobile interior decoration PVC material of thermoplasticity

Also Published As

Publication number Publication date
CN110256787A (en) 2019-09-20

Similar Documents

Publication Publication Date Title
US20080108755A1 (en) Microgel-containing composition
KR100199087B1 (en) Thermoplastic pvc foaming composition
US4290927A (en) Vulcanizable polyblend
JPH02124958A (en) Thermoplastic polyvinyl chloride elastomer composition
JPS62230838A (en) Elastic plastic composition
JPH09268239A (en) Low-exothermic rubber composition and roll thereof
KR20130099191A (en) Plastisol for spray-molded plastic articles
WO2021012888A1 (en) Thermoplastic cold-resistant pvc material for automobile interior decoration
WO2021012896A1 (en) Low-temperature wear-resistant automotive interior material
JP2002053729A (en) Impact modifier improved in blocking resistance
JPH08225702A (en) Thermoplastic composition based on polyvinylidene fluoride
JP2011032472A (en) Low temperature pvc for seamless type air bag door with little voc and clouding
JP2018044113A (en) Thermoplastic elastomer composition
JP2018044115A (en) Thermoplastic elastomer composition
KR101012173B1 (en) Polyvinyl halide-uncrosslinked elastomer alloy
JPS6092345A (en) Vinyl chloride resin composition
JP2018044114A (en) Thermoplastic elastomer composition
JP5895515B2 (en) Thermoplastic resin composition and molded article thereof
WO2021012889A1 (en) Modified impact resistant rigid pvc material
JP2010111877A (en) Foam rubber containing softening agent and method for producing the same
JP2001114920A (en) Crosslinked foamed item and its preparation method
JPH087685A (en) Grommet
JPS6040148A (en) Thermoplastic elastomer composition
JPS63309546A (en) Production of elastomer composition
JP2970464B2 (en) Method for producing thermoplastic elastomer composition

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: 20843285

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20843285

Country of ref document: EP

Kind code of ref document: A1