WO2014019109A1 - 应用于聚氯乙烯管材、管件的加工改性剂 - Google Patents

应用于聚氯乙烯管材、管件的加工改性剂 Download PDF

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WO2014019109A1
WO2014019109A1 PCT/CN2012/001406 CN2012001406W WO2014019109A1 WO 2014019109 A1 WO2014019109 A1 WO 2014019109A1 CN 2012001406 W CN2012001406 W CN 2012001406W WO 2014019109 A1 WO2014019109 A1 WO 2014019109A1
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weight
polyvinyl chloride
parts
pipe
monomer composition
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PCT/CN2012/001406
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English (en)
French (fr)
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田岳南
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Tian Yuenan
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to a polyvinyl chloride pipe, a processing modifier for a pipe member, and a polyvinyl chloride resin composition using the same, which is used for producing pipes, pipe fittings, and more particularly Processing modifier for extrusion and injection molding.
  • the processing modifier provides plasticization during extrusion molding of the polyvinyl chloride resin without impairing the inherent properties of the polyvinyl chloride resin, and greatly increases the hardness increase that is difficult to achieve by conventional processing aids, and also improves The heat resistance of the polyvinyl chloride pipe fittings.
  • Polyvinyl chloride resin has been widely used in construction, packaging, industrial and agricultural production, transportation, communication and people's daily necessities due to its excellent mechanical strength, corrosion resistance and flame retardancy.
  • profiles, pipes and fittings used in construction projects are mostly used.
  • Polyvinyl chloride pipes and fittings are generally limited in terms of heat resistance, impact strength, processing fluidity, low temperature toughness, hardness and other processing properties and mechanical properties due to limitations in raw material components and polymerization processes. problem.
  • the hardness of the polyvinyl chloride pipe and the pipe member is poor, and the heat resistance stability is poor, which is difficult to solve.
  • ACR can promote PVC gelation, improve the fluidity of the melt, thereby improving the heat strength and elongation of the melt, and improving The internal and surface quality of the product; at the same time shortening the melting time and increasing production efficiency.
  • PVC processing aid ACR can promote PVC gelation, improve the fluidity of the melt, thereby improving the heat strength and elongation of the melt, and improving The internal and surface quality of the product; at the same time shortening the melting time and increasing production efficiency.
  • the polyvinyl chloride pipe, the pipe member is soft, and the heat resistance stability is poor.
  • a polyvinyl chloride processing modifier capable of remarkably improving the hardness and heat resistance of a polyvinyl chloride pipe, a pipe product, and a preparation method thereof are expected.
  • the object of the present invention is to avoid the above-mentioned deficiencies in the prior art, and to provide a polyvinyl chloride which can significantly improve the hardness and heat stability of the polyvinyl chloride processing modifier, thereby modifying the polyvinyl chloride.
  • Pipe fittings and pipe products have high hardness and heat resistance.
  • the object of the present invention can be achieved by the following measures:
  • the emulsifier used in emulsion polymerization is sodium dodecyl diphenyl ether disulfonate, which has adsorption capacity compared with traditional sulfhydryl sulfate, alkyl phosphate, polyoxyethylene decyl ether and polyoxyethylene alkyl fatty acid ester. Strong, strong dispersion, strong connection and so on.
  • the polymerizable monomer composition is a total weight component composed of 70-85 parts by weight of styrene monomer, 10-20 parts by weight of acrylonitrile monomer, and 0-10 parts by weight of n-butyl methacrylate.
  • the polymerization method was as follows: The air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen. Next, 100 parts by weight of deionized water and 4-5 parts by weight of sodium dodecyl diphenyl ether disulfonate are added, and stirred uniformly, 35-43 parts by weight of styrene monomer, 5-7 parts by weight of propylene. A nitrile monomer, 0-5 parts by weight of a n-butyl methacrylate monomer composition is put therein, and then the air in the reactor is replaced with nitrogen, and then the reactor is heated to 55 ° C under stirring, and 0.04- is added.
  • the pre-emulsified monomer composition the monomer composition comprising 35-43 parts by weight of benzene Ethylene monomer, 5-7 parts by weight of acrylonitrile monomer, 0-5 parts by weight of n-butyl methacrylate, 2-3 parts by weight of sodium dodecyl diphenyl ether disulfonate 0.02-0.03 parts by weight
  • the potassium persulfate and 50 parts by weight of deionized water are emulsified at a high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction was carried out by dropping in 90-100 minutes.
  • the reaction temperature was controlled below 75 °C.
  • 7 TC was thermostated for 1 hour, then heated to 85 ⁇ for 30 minutes, and cooled with cooling water until The polymer emulsion obtained under 40 , is dried to obtain a processing modifier for polyvinyl chloride pipe and pipe fittings.
  • the intrinsic viscosity of the processing modifier is measured by using chloroform as a solvent at a temperature of 25 ⁇ 0.1 °C. It is 6.0-7.0.
  • the emulsifier used in the present invention is sodium dodecyl diphenyl ether disulfonate, which is superior to conventional mercapto sulfate, mercapto phosphate, polyoxyethylene mercapto ether, polyoxyethylene alkyl fatty acid.
  • the ester has the characteristics of strong adsorption capacity, large dispersing power and strong bonding force.
  • the amount used is 5-8% of the amount of comonomer.
  • the oxidizing agent used in the present invention includes ammonium, sodium or potassium persulfate and t-butyl hydroperoxide.
  • the most preferred oxidizing agent is potassium persulfate.
  • the amount used is 0.05-0.1% by weight of the comonomer.
  • Embodiment 1 The air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen. Next, 100 parts by weight of deionized water and 4 parts by weight of sodium dodecyl diphenyl ether disulfonate were added, and 41 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, and 2 parts by weight were uniformly stirred. The n-butyl methacrylate monomer composition is put into it.
  • the air in the reactor was replaced with nitrogen, and then the reactor was heated to 55 Torr under mashing, and 0.04 part by weight of potassium persulfate was added to carry out a reaction, and the reaction temperature was controlled to be less than 73 ° C, and the temperature was lowered to 60 Torr or less.
  • the second monomer composition monomer composition pre-emulsified includes 41 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, 2 parts by weight of n-butyl methacrylate, and 4 parts by weight.
  • a portion of sodium dodecyl diphenyl ether disulfonate, 0.04 parts by weight of potassium persulfate, and 50 parts by weight of deionized water were emulsified at high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction is carried out by dropwise addition within 90-100 minutes, the reaction temperature is controlled below 75 ° C, and the temperature is maintained at 70 ° C for 1 hour after the completion of the dropwise addition, and then the temperature is raised to 85 ⁇ for 30 minutes, and the temperature is lowered by using the cooling water to
  • the polymer emulsion obtained under 40 is dried to obtain a processing modifier for polyvinyl chloride pipes and tubes.
  • the intrinsic viscosity of the processing modifier was 6.7 using chloroform as a solvent at a temperature of 25 ⁇ 0.1 °C.
  • the air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen.
  • 100 parts by weight of deionized water and 4 parts by weight of sodium dodecyl diphenyl ether disulfonate were added, and 40 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, and 3 parts by weight were uniformly stirred.
  • the n-butyl methacrylate monomer composition is put into it.
  • the air in the reactor was replaced with nitrogen, and then the reactor was heated to 55 ° C under stirring, and 0.04 parts by weight of potassium persulfate was added to carry out a reaction, and the reaction temperature was controlled to be less than 73 ⁇ , and the temperature was lowered to below 60 ° C. .
  • the pre-emulsified second monomer composition monomer composition comprises 40 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, 3 parts by weight of n-butyl methacrylate, 4 weights A portion of sodium dodecyl diphenyl ether disulfonate, 0.04 parts by weight of potassium persulfate, and 50 parts by weight of deionized water were emulsified at high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction is carried out by dropwise addition within 90-100 minutes, the reaction temperature is controlled below 75 ° C, and the temperature is maintained at 70 ° C for 1 hour after the completion of the dropwise addition, and then the temperature is raised to 85 ° C for 30 minutes, and the water is cooled.
  • the polymer emulsion obtained by cooling to 40 ° C or lower is dried to obtain a processing modifier for polyvinyl chloride pipes and tubes.
  • the intrinsic viscosity of the processing modifier was 6.8 using chloroform as a solvent at a temperature of 25 ⁇ 0.1 °C.
  • the air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen.
  • 100 parts by weight of deionized water and 4 parts by weight of sodium dodecyl diphenyl ether disulfonate were added, and 38 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, and 5 parts by weight were uniformly stirred.
  • the n-butyl methacrylate monomer composition is put into it.
  • the air in the reactor was replaced with nitrogen, and then the reactor was heated to 55 ° C under stirring, and 0.04 parts by weight of potassium persulfate was added to carry out a reaction, and the reaction temperature was controlled to be less than 73 ° C, and the temperature was lowered to below 60 ° C. .
  • the pre-emulsified second monomer composition monomer composition comprises 38 parts by weight of styrene monomer, 7 parts by weight of acrylonitrile monomer, 5 parts by weight of n-butyl methacrylate, 4 weights A portion of sodium dodecyl diphenyl ether disulfonate, 0.04 parts by weight of potassium persulfate, and 50 parts by weight of deionized water were emulsified at high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction is carried out by dropwise addition within 90-100 minutes, the reaction temperature is controlled below 75 ° C, and the temperature is maintained at 70 ° C for 1 hour after the completion of the dropwise addition, and then the temperature is raised to 85 ° C for 30 minutes, and the water is cooled.
  • the polymer emulsion obtained by cooling to 40 ° C or lower is dried to obtain a processing modifier for polyvinyl chloride pipes and tubes.
  • the intrinsic viscosity of the processing modifier was 6.9 using chloroform as a solvent at a temperature of 25 ⁇ 0.1 °C.
  • the air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen.
  • 100 parts by weight of deionized water and 4 parts by weight of sodium dodecyl diphenyl ether disulfonate were added, and evenly stirred, 35 parts by weight of styrene monomer, 10 parts by weight of acrylonitrile monomer, and 5 parts by weight.
  • the n-butyl methacrylate monomer composition is put into it.
  • the air in the reactor was replaced with nitrogen, then the reactor was heated to 55 ° C under stirring, 0.04 parts by weight of potassium persulfate was added to react, and the reaction temperature was controlled to be less than 73 ° C, and the temperature was lowered to below 60 ° C. .
  • the second monomer composition monomer composition pre-emulsified includes 35 parts by weight of styrene monomer, 10 parts by weight of acrylonitrile monomer, 5 parts by weight of n-butyl methacrylate, and 4 parts by weight.
  • a portion of sodium dodecyl diphenyl ether disulfonate, 0.04 parts by weight of potassium persulfate, and 50 parts by weight of deionized water are emulsified at high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction is carried out by dropping in 90-100 minutes, the reaction temperature is controlled below 75 ,, and the temperature is kept at 70 ° C for 1 hour after the completion of the dropwise addition, and then the temperature is raised to 85 ° C for 30 minutes, and the temperature is lowered by using the cooling water to
  • the polymer emulsion obtained under 40 is dried to obtain a processing modifier for polyvinyl chloride pipes and tubes.
  • the intrinsic viscosity of the processing modifier was 6.4 using chloroform as a solvent at a temperature of 25 ⁇ 0.1 Torr.
  • the air in the reactor provided with the agitator and the reflux condenser was replaced with nitrogen.
  • 100 parts by weight of deionized water and 4 parts by weight of sodium dodecyl diphenyl ether disulfonate were added, and 43 parts by weight of styrene monomer, 5 parts by weight of acrylonitrile monomer, and 2 parts by weight were uniformly stirred.
  • the n-butyl methacrylate monomer composition is put into it.
  • the air in the reactor was replaced with nitrogen, and then the reactor was heated to 55 ° C under stirring, and 0.04 parts by weight of potassium persulfate was added to react, and the reaction temperature was controlled to be less than 73 ° C, and the temperature was lowered to below 60 ° C. .
  • the second monomer composition monomer composition pre-emulsified includes 43 parts by weight of styrene monomer, 5 parts by weight of acrylonitrile monomer, 2 parts by weight of n-butyl methacrylate, and 4 parts by weight.
  • a portion of sodium dodecyl diphenyl ether disulfonate, 0.04 parts by weight of potassium persulfate, and 50 parts by weight of deionized water were emulsified at high speed for 0.5-1 hour to form a stable emulsion.
  • the second reaction is carried out by dropwise addition within 90-100 minutes.
  • the reaction temperature is controlled below 75 °C.
  • the temperature is maintained at 70 ° C for 1 hour, and then the temperature is raised to 85 ° C for 30 minutes.
  • the polymer emulsion obtained by cooling to below 40 ° C, and then dried A processing modifier for polyvinyl chloride pipes and pipe fittings is obtained.
  • the intrinsic viscosity of the processing modifier was 6.2 using chloroform as a solvent at a temperature of 25 ⁇ 0.1 °C.
  • a process modifier was prepared in the same manner as in Example 1, except that n-butyl methacrylate in Example 1 was not used, and the obtained process modifier had an intrinsic viscosity of 6.0.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

一种用于聚氯乙烯管材、管件的加工改性剂和使用该加工助剂的聚氯乙烯树脂组合物。用于聚氯乙烯管材、管件的加工改性剂采用两段乳液聚合工艺方法，乳液聚合采用十二烷基二苯醚二磺酸钠；第一段单体组合物占总单体的50wt%，第二段单体组合物占总单体的50wt%；第二段单体组合物采用预乳化滴加的方法：聚合温度控制在55-75°C，制备共聚乳液，乳液再经喷雾干燥后，制得固体粉末产品；其中第一段、第二段单体组合物总重量为100%计，苯乙烯为70-85%，丙烯腈为10-20%，甲基丙烯酸正丁酯为0-10%，得到的聚合物能够显著提高聚氯乙烯管材、管件加工改性剂产品的硬度和耐热稳定性。

Description

说 明 书 应用于聚氯乙烯管材、 管件的加工改性剂 技术领域
[0001] 本发明涉及用于聚氯乙烯管材、 管件的加工改性剂和使用该加工助剂的聚氯乙烯树脂 组合物， 该聚氯乙烯树脂用于生产管材、 管件， 更具体涉及用于挤出、 注塑的加工改性剂。 该加工改性剂在挤出注塑聚氯乙烯树脂期间提供促进塑化作用而不损害聚氯乙烯树脂固有的 性能， 并且可大大提高通过常规加工助剂很难做到的硬度增加， 同时还改进了聚氯乙烯管材 管件的耐热稳定性。
背景技术
[0002] 聚氯乙烯树脂以其优良的机械强度、 耐腐蚀性、难燃性， 在建筑、包装、 工农业生产、 交通、通讯和人民生活用品等方面获得了广泛的使用。特别在建筑工程中用到的型材、管材、 管件居多。 聚氯乙烯管材、 管件由于受到原料组分、 聚合工艺等诸多局限， 在耐热稳定性、 耐冲击强度、 加工流动性、 低温韧性、 硬度等加工性能和力学性能方面普遍存在不能满足用 户需求的问题。 特别在聚氯乙烯管材、 管件的硬度较差， 耐热稳定性较差成为难以解决的问 题。
[0003] 在聚氯乙烯管材、 管件加工过程中， 添加 PVC加工助剂 ACR， ACR能够促进 PVC 凝胶化， 使熔体的流动性得到改善， 从而提高熔体的热强度及延伸性， 改善制品的内部和表 面质量； 同时缩短了熔融时间， 提高了生产效率。 但是不能从根本解决聚氯乙烯管材、 管件 发软、 耐热稳定性差的问题。
[0004] 一种能够显著提高聚氯乙烯管材、 管件产品硬度、 耐热稳定性好的聚氯乙烯加工改性 剂及其制备方法， 是人们所期待的。
发明内容
【0005〗 本发明的目的在于避免上述现有技术中的不足之处， 而提供一种能够显著提高聚氯乙 烯加工改性剂的硬度及耐热稳定性， 从而使改性后的聚氯乙烯管件、 管材产品具有高的硬质 和耐热性能。
[0006] 本发明的目的可以通过如下措施来达到：
本发明的用于聚氯乙烯管材、 管件的加工改性剂， 其特征在于：
乳液聚合采用的乳化剂为十二垸基二苯醚二磺酸钠， 比传统的垸基硫酸盐、烷基磷酸盐 、聚 氧乙烯垸基醚、 聚氧乙烯烷基脂肪酸酯具有吸附能力强， 分散力大， 连接力强等特点。
[0007] 采用两段乳液聚合工艺方法， 其中第二段采用预乳化滴加的方式， 采用两段乳液聚合 工艺保证了超高分子量、 硬度、 耐热稳定性的加工改性剂。 [0008] 其聚合单体组合物为由 70-85重量份的苯乙烯单体， 10-20重量份的丙烯腈单体以及 0-10重量份的甲基丙烯酸正丁酯组成的总重量份为 100的聚合单体组合物。
【0009】 其聚合方法如下： 将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着 将 100重量份去离子水和 4-5重量份的十二烷基二苯醚二磺酸钠加入， 搅拌均匀， 将 35-43 重量份的苯乙烯单体、 5-7重量份的丙烯腈单体、 0-5重量份的甲基丙烯酸正丁酯单体组合物 投入其中， 然后将反应器中的空气用氮气置换， 接着将反应器在搅拌下加热至 55 °C， 加入 0.04-0.05重量份的过硫酸钾， 使之进行反应， 控制反应温度小于 73°C， 降温至 60°C以下； 将预先乳化好的单体组合物， 单体组合物包括 35-43重量份的苯乙烯单体、 5-7重量份的丙烯 腈单体、 0-5重量份的甲基丙烯酸正丁酯、 2-3重量份的十二烷基二苯醚二磺酸钠 0.02-0.03重 量份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。在 90— 100 分钟内采用滴加的方式进行第二段反应， 反应温度控制在 75 °C以下， 滴加完毕后 7(TC恒温 1 小时， 后升温至 85Ό熟化 30分钟， 用降温水降温至 40Ό以下得到的聚合物乳液， 再经干燥 即得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 °C温度下测量， 该 加工改性剂的特性粘度为 6.0-7.0。
[0010] 用于本发明的乳化剂为十二垸基二苯醚二磺酸钠， 比传统的垸基硫酸盐、 垸基磷酸 盐 、聚氧乙烯垸基醚、聚氧乙烯烷基脂肪酸酯具有吸附能力强，分散力大，连接力强等特点。 用量为共聚单体用量的 5-8%。
[0011] 用于本发明的氧化剂包括铵、 钠或钾的过硫酸盐和叔丁基过氧化氢。 最优选的氧化剂 为过硫酸钾。 用量为共聚单体重量的 0.05-0.1%。
[0012] 本发明的技术方案相比现有技术具有突出的实质性特点和显著的进步， 技术方案实施 后， 将产生如下积极效果：
(1)、 提供了一种能够显著提高聚氯乙烯管材、 管件加工改性剂产品的硬度和耐热稳定性， 使 改性后的聚氯乙烯管材、 管件具有高的硬度和耐热稳定性。
[0013] (2)、 采用新型的乳化剂十二烷基二苯醚二磺酸钠， 使加工改性剂粒径大小分布窄而均 匀、 稳定性高， 解决了产品的硬度和耐热性的问题。
[0014] (3)、 采用两段乳液聚合工艺的方法， 其中第二段采用乳化滴加的方式， 合适的单体配 比及与之匹配的助剂制备了超高分子量， 并且分子量分布较窄的聚合物。
[0015] (4), 用于聚氯乙烯其它材料中， 由于该聚合物的玻璃化温度高于聚氯乙烯的玻璃化温 度， 可作为聚氯乙烯的耐热改性使用。
具体实施方式
[0016] 实施例 1 将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着将 100重量份去离子水和 4重量份的十二垸基二苯醚二磺酸钠加入， 搅拌均匀将 41重量份的苯乙烯单体， 7重量份的 丙烯腈单体， 2 重量份的甲基丙烯酸正丁酯单体组合物投入其中。 然后将反应器中的空气用 氮气置换，接着将反应器在撹拌下加热至 55 Γ ,加入 0.04重量份的过硫酸钾，使之进行反应， 控制反应温度小于 73°C， 降温至 60Ό以下。
[0017] 将预先乳化好的第二单体组合物单体组合物包括 41重量份的苯乙烯单体、 7重量份的 丙烯腈单体、 2重量份的甲基丙烯酸正丁酯、 4重量份的十二烷基二苯醚二磺酸钠、 0.04重量 份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。 在 90-100分 钟内采用滴加的方式进行第二段反应， 反应温度控制在 75°C以下， 滴加完毕后 70°C恒温 1小 时， 后升温至 85Ό熟化 30分钟， 用降温水降温至 40Ό以下得到的聚合物乳液， 再经干燥即 得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 °C温度下测量， 该加 工改性剂的特性粘度为 6.7。
[0018】 实施例 2
将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着将 100重量份去离子水和 4重量份的十二垸基二苯醚二磺酸钠加入， 搅拌均匀将 40重量份的苯乙烯单体， 7重量份的 丙烯腈单体， 3 重量份的甲基丙烯酸正丁酯单体组合物投入其中。 然后将反应器中的空气用 氮气置换，接着将反应器在搅拌下加热至 55°C，加入 0.04重量份的过硫酸钾，使之进行反应， 控制反应温度小于 73Ό , 降温至 60°C以下。
[0019] 将预先乳化好的第二单体组合物单体组合物包括 40重量份的苯乙烯单体、 7重量份的 丙烯腈单体、 3重量份的甲基丙烯酸正丁酯、 4重量份的十二烷基二苯醚二磺酸钠、 0.04重量 份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。 在 90-100分 钟内采用滴加的方式进行第二段反应， 反应温度控制在 75°C以下， 滴加完毕后 70°C恒温 1小 时， 后升温至 85°C熟化 30分钟， 用降温水降温至 40°C以下得到的聚合物乳液， 再经干燥即 得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 °C温度下测量， 该加 工改性剂的特性粘度为 6.8。
[0020] 实施例 3
将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着将 100重量份去离子水和 4重量份的十二垸基二苯醚二磺酸钠加入， 搅拌均匀将 38重量份的苯乙烯单体， 7重量份的 丙烯腈单体， 5 重量份的甲基丙烯酸正丁酯单体组合物投入其中。 然后将反应器中的空气用 氮气置换，接着将反应器在搅拌下加热至 55°C，加入 0.04重量份的过硫酸钾，使之进行反应， 控制反应温度小于 73°C， 降温至 60Ό以下。 [0021] 将预先乳化好的第二单体组合物单体组合物包括 38重量份的苯乙烯单体、 7重量份的 丙烯腈单体、 5重量份的甲基丙烯酸正丁酯、 4重量份的十二烷基二苯醚二磺酸钠、 0.04重量 份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。 在 90-100分 钟内采用滴加的方式进行第二段反应， 反应温度控制在 75°C以下， 滴加完毕后 70°C恒温 1小 时， 后升温至 85°C熟化 30分钟， 用降温水降温至 40°C以下得到的聚合物乳液， 再经干燥即 得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 °C温度下测量， 该加 工改性剂的特性粘度为 6.9。
【0022】 实施例 4
将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着将 100重量份去离子水和 4重量份的十二烷基二苯醚二磺酸钠加入，搅拌均匀将 35重量份的苯乙烯单体， 10重量份的 丙烯腈单体， 5 重量份的甲基丙烯酸正丁酯单体组合物投入其中。 然后将反应器中的空气用 氮气置换，接着将反应器在搅拌下加热至 55°C ,加入 0.04重量份的过硫酸钾，使之进行反应， 控制反应温度小于 73°C， 降温至 60Γ以下。
【0023】 将预先乳化好的第二单体组合物单体组合物包括 35重量份的苯乙烯单体、 10重量份 的丙烯腈单体、 5重量份的甲基丙烯酸正丁酯、 4重量份的十二垸基二苯醚二磺酸钠、 0.04重 量份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。 在 90-100 分钟内采用滴加的方式进行第二段反应， 反应温度控制在 75Ό以下， 滴加完毕后 70°C恒温 1 小时， 后升温至 85°C熟化 30分钟， 用降温水降温至 40Ό以下得到的聚合物乳液， 再经干燥 即得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 Ό温度下测量， 该 加工改性剂的特性粘度为 6.4。
[0024] 实施例 5
将设置有搅拌器和回流冷凝器的反应器中的空气用氮气置换。 接着将 100重量份去离子水和 4重量份的十二烷基二苯醚二磺酸钠加入， 搅拌均匀将 43重量份的苯乙烯单体， 5重量份的 丙烯腈单体， 2 重量份的甲基丙烯酸正丁酯单体组合物投入其中。 然后将反应器中的空气用 氮气置换，接着将反应器在搅拌下加热至 55°C ,加入 0.04重量份的过硫酸钾，使之进行反应， 控制反应温度小于 73 °C , 降温至 60Ό以下。
[0025] 将预先乳化好的第二单体组合物单体组合物包括 43重量份的苯乙烯单体、 5重量份的 丙烯腈单体、 2重量份的甲基丙烯酸正丁酯、 4重量份的十二烷基二苯醚二磺酸钠、 0.04重量 份的过硫酸钾、 50重量份的去离子水高速搅拌乳化 0.5-1小时， 形成稳定乳液。 在 90-100分 钟内采用滴加的方式进行第二段反应， 反应温度控制在 75 °C以下， 滴加完毕后 70°C恒温 1小 时， 后升温至 85°C熟化 30分钟， 用降温水降温至 40°C以下得到的聚合物乳液， 再经干燥即 得到用于聚氯乙烯管材、 管件的加工改性剂。 以氯仿为溶剂， 在 25 ±0.1 °C温度下测量， 该加 工改性剂的特性粘度为 6.2。
[0026] 比较例 1
在聚氯乙烯树脂组合物中不加入加工改性剂进行挤出注塑评估。
[0027] 比较例 2
按与实施例 1相同的方式制备加工改性剂， 但不使用实施例 1中的甲基丙烯酸正丁酯， 获得 的加工改性剂的特性粘度为 6.0。
[0028] 产品性能：
将上述实施例 1-5和比较例 1-2所得的成品按照下列 2中配方分别在高速混料机中混至 110Ό 出料冷却，后在挤出温度 170°C的条件下做挤出注塑成型试验，分别对 PVC管材和 PVC管件 进行检测， 检测结果如表 1。
[0029] PVC管材配方
Figure imgf000006_0001
1. PVC管件配方
Figure imgf000006_0002
表 1试验测试结果
实施例实施例实施例实施例对比对比例
■ l！i 2 3 4 5 例 1 2
特性粘 1
度 （厘 te. 7 6. 8 6. 9 6. 4 6. 2 1 6. 0
泊）
PVC管材较好 较好 较好 好 好 较差差 硬度
PVC管材
耐热稳 较好 较好 较好 好 好 较差 定性
PVC管件
较好 较好 较好 好 好 较差 硬度
PVC管件
耐热稳 较好 较好 较好 好 好 较差 差 定性

Claims

权 利 要 求 书
1. 一种用于聚氯乙烯管材、 管件的加工改性剂， 其特征在于： 采用两段乳液聚合工艺方 法， 乳液聚合采用十二垸基二苯醚二磺酸钠； 第一段单体组合物占总单体的 50wt%， 第二段 单体组合物占总单体的 50wt%； 第二段单体组合物采用预乳化滴加的方法： 聚合温度控制在 55-75'C , 制备共聚乳液， 乳液再经喷雾干燥后， 制得固体粉末产品； 其中第一段、 第二段单 体组合物总重量为 100%计，苯乙烯为 70-85%，丙烯腈为 10-20%，甲基丙烯酸正丁酯为 0-10%。
2.按照权利要求 1的用于聚氯乙烯管材、 管件的加工改性剂， 其特征在于： 十二烷基二 苯醚二磺酸钠用量为共聚单体重量的 5-8%。
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