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CN1012371B - 一种偶联剂的制法 - Google Patents

一种偶联剂的制法

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Publication number
CN1012371B
CN1012371B CN89102500A CN89102500A CN1012371B CN 1012371 B CN1012371 B CN 1012371B CN 89102500 A CN89102500 A CN 89102500A CN 89102500 A CN89102500 A CN 89102500A CN 1012371 B CN1012371 B CN 1012371B
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China
Prior art keywords
coupling agent
rcoo
composite material
atoms metal
polyvinyl chloride
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Expired
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CN89102500A
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English (en)
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CN1042722A (zh
Inventor
辛树祥
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Nanjing University
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Nanjing University
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Publication of CN1042722A publication Critical patent/CN1042722A/zh
Publication of CN1012371B publication Critical patent/CN1012371B/zh
Expired legal-status Critical Current

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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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/932—Blend of matched optical properties

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  • 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

在聚氯乙烯复合材料的配方中，用(RCOO)aM(OX)b[其中R为烃基；M为金属元素；X为磷酰基或磺酰基]代替常用的单烷氧型钛酸酯偶联剂，有良好的物料间的相容性和流变性。此种偶联剂对无机填料的种类和含水量无特殊要求，且成本低。复合材料成型后其拉伸强度与伸长率都不低于用ND-102偶联剂的复合材料。叙述了此种偶联剂的合成方法。

Description

本发明属于一类聚氯乙烯复合材料的配方。
聚氯乙烯树脂中常加入无机填料以改善其力学性能和减少制品的树脂用量，但无机填料和树脂间的相容性差，树脂加入无机填料后，加工时的流变性小，给加工带来困难。目前的配方是加入单烷氧型钛酸酯偶联剂以改善物料间的相容性和加工时的流变性。此类钛酸酯含有一个水解基团〔如异丙氧基〕，因此对无机填料的含水量有较严格的要求，并且单烷氧型钛酸酯的成本较高。
本发明的目的在于提供一类对无机填料含水量的要求不严格的，成本较低的聚氯乙烯复合材料的配方。
本发明提供了一类聚氯乙烯复合材料的配方，其特征是将以化学式（RCOO）aM（OX）b为代表的物质代替钛酸酯加入到树脂，无机填料或其它助剂的配料中，以改善物料之间的相容性和加工时的流变性。在式（RCOO）aM（OX）b中，M中心原子可以为Ca、Sr、Ba、Al、Sn、Pb、Mn、Fe、Ti、Zr、Sb、Bi、V、Cu、Cr、Co、Ni、Zn、Cd等金属元素，R可以为C7-C21饱和或不饱和的烃基或者芳香族烃基，X可以为二异辛氧基磷酰基
Figure 89102500_IMG2
、十二烷基苯磺酰基、或
Figure 89102500_IMG3
基团，b≥a，a≥0，且a+b＝n，n为金属原子M的氧化数。此类物质可以在pH＝6-11的水溶液中，于室温至100℃之间，将相当于M（OH）n的化合物与RCOOH和磷酸二异辛酯作用制得：
Figure 89102500_IMG4
由于（RCOO）aM（OX）b中不含有水解基团，因此对无机填料的种类和其含水量均无特殊要求，且成本比钛酸酯低得多。它使无机填料与树脂间的相容性改善，流变性增加，在1000份CaCO3和1500份矿物油中含有5份（RCOO）aM（OX）b时，体系的粘度如下（表见文后）：
在本配方中若加入环氧大豆油，可以减少或代替热稳定剂铅盐的用量。
以下通过具体实施例进一步说明本发明内容。
例1，在500ml水中加入Fe2O380克，油酸282克和磷酸二异辛酯644克，搅拌均匀，在80～90℃下反应1小时后，除去水层，干燥后得C17H33COOFe- 它为棕色固体，熔点为110-124℃。
例2、在500ml水中加入Al2（SO4）3·18H2O333克，搅拌，然后加入NaHCO3，调节pH＝6～8，加入油酸282克，磷酸二异辛酯644克，搅拌均匀，在50～80℃下反应二小时后，除去水层，用去离子水洗至无SO2- 4存在，干燥后得
Figure 89102500_IMG6
，它为白色固体，熔点为141.8～148℃。
例3、聚氯乙烯复合材料配方：PVC（三型）[镇江树脂厂生产]：100份;轻质CaCO3（320目全通过）[南京跃进炼灰厂生产]：100份;三盐：5份;硬脂酸铅：1份;硬脂酸钡：1.5份;DOP：20份;
Figure 89102500_IMG7
：1份，配料后，在198℃加工成型，其拉伸强度横向为204.9kg/cm2;纵向为226.2kg/cm2（用ND-102偶联剂分别为202.1kg/cm2和238.9kg/cm2），其伸长率横向为10.0%;纵向为15.2%（用ND-102偶联剂分别8.8%和11.2%）。
试样 空白 Ca（OX）2Zn（OX）2Fe（OX）3
粘度（厘泊）    15000    600    600    680
C17H33COOFe（OX）2ND-102
260    420

Claims (2)

1、一种用于聚氯乙烯复合材料的偶联剂(RCOO)aM(OX)b，其中R可以为C7-C21饱和或不饱和脂肪族烃基或者芳香族烃基，M为金属原子，X为二异辛氧基磷酰基 ，b≤a，a≥0，且a+b=n，n为金属原子M的氧化数，其特征是它可以在pH=6-11的水溶液中，于室温至100℃之间，由相当于M(OH)n的化合物与RCOOH和磷酸二异辛酯作用制得。
2、根据权利要求1所述的偶联剂（RCOO）aM（OX）b，其特征是M可以为Ca、Sr、Ba、Al、Sn、Pb、Mn、Fe、Ti、Zr、Sb、Bi、V、Cu、Co、Ni、Zn、Cd金属原子。
CN89102500A 1985-04-01 1985-04-01 一种偶联剂的制法 Expired CN1012371B (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN85102666.4A CN1005982B (zh) 1985-04-01 1985-04-01 一类聚氯乙烯复合材料的配方

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
CN85102666.4A Division CN1005982B (zh) 1985-04-01 1985-04-01 一类聚氯乙烯复合材料的配方
CN85102666 Division 1985-04-01

Publications (2)

Publication Number Publication Date
CN1042722A CN1042722A (zh) 1990-06-06
CN1012371B true CN1012371B (zh) 1991-04-17

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Family Applications (2)

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69700223T2 (de) * 1996-04-30 1999-12-09 Samsung Electronics Co. Ltd., Suwon Schaltung zur Regelung der Drehzahl eines Rotationsmotors
CN102504335A (zh) * 2011-12-19 2012-06-20 牟作峰 一种偶联剂的制备方法

Also Published As

Publication number Publication date
CN85102666A (zh) 1986-09-24
CN1042722A (zh) 1990-06-06
CN1005982B (zh) 1989-12-06

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