CN1080293A - 珠状可发性苯乙烯聚合物的生产方法 - Google Patents

珠状可发性苯乙烯聚合物的生产方法 Download PDF

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CN1080293A
CN1080293A CN93106865A CN93106865A CN1080293A CN 1080293 A CN1080293 A CN 1080293A CN 93106865 A CN93106865 A CN 93106865A CN 93106865 A CN93106865 A CN 93106865A CN 1080293 A CN1080293 A CN 1080293A
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styrene
polymer
benzene
peroxidation
temperature section
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P·霍尔茨边耶
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Huels AG
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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
    • C08F12/00—Homopolymers and 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
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08J9/16—Making expandable particles
    • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
    • 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
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • 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
    • C08J2325/00—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
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

用那些已知的工艺方法生产的珠状可发性苯乙 烯聚合物中仍含有相当多的苯。根据本发明的工艺 方法，可生产出苯浓度非常低的苯乙烯聚合物。根据 本发明生产的苯乙烯聚合物经发泡可得到泡沫颗粒 状物。

Description

本发明涉及一种生产粒状、含液体发泡剂的苯乙烯聚合物（EPS）的方法，所述聚合物在未加工的颗粒中苯浓度明显较低，产品中的残余单体含量地降低了。
苯乙烯聚合物的粒状泡沫体在  装领域获得相当重要的工业用途。更具体地说，如热绝缘材料。它们的工业化生产可通过加入一种液体发泡剂用悬浮法聚合苯乙烯得到。在加工过程中，这种可发性苯乙烯聚合物首先被加热发泡形成泡沫颗粒，然后在一个闭合的模具中熔融成型。
生产可发生苯乙烯聚合物的苯乙烯悬浮聚合法常常是一个不连续的过程。它有两个不同的温度段以及两种有不同半衰期的过氧化物作为聚合引发剂。为了获得心可能低的残留单体含量，常常在第一聚合段用过氧化二苯甲酰于80℃到90℃聚合，然后在第二聚合段用能在更高温度下分解的过苯甲酸特丁酯于105℃至130℃下聚合。
此方法的缺点是用此法制得的可发性苯乙烯聚合物中苯的重量百分比为0.002%到0.01%，通常在0.003%到0.005%之间。在后处理过程中，对苯乙烯聚合物进行加热，则苯含量的70%到80%可释出。在最后的成型制品中苯的重量百分比引应还有0.0005%到0001%。
因此，本发明的目的就是生产苯含量明显降低的可发性苯乙烯聚合物。使在后处理过程中减去不必要的苯的释出处理，并且能制得基本上不含苯的发泡模塑物。
令人惊喜的是，现在发现这个目的可以用另一种不同的能溶解苯的过氧化物来取代苯乙烯悬浮聚合法中的第二个引发剂而实现。脂肪族和环状脂肪族的过氧化缩酮类，具体地说，如2，2-双（叔丁基过氧）丁烷和1，1-双（叔丁基过氧）环己烷以及单过氧化碳酸酯类，具体地说，如过氧碳酸2-乙基己基叔戊酯和过氧碳酸2-乙基己基叔丁酯，都被证实特别适用。
在日本两个已发表的专利说明书56167706和60031536中已知在苯乙烯悬浮聚合法中引发剂是使用单官能团的或双官能团的非芳香烃。然而，这些文章中指出使用这些引发剂并不是为了降低聚合物中苯的浓度，而是，譬如说，获得一种特定的分子量分布。
根据本发明，通过使用上述引发剂的任意一种，都可以使粒状苯乙烯聚合物中苯的含量降低到重量比＜0.0005%。而由此经发泡制得的聚苯乙烯发泡模塑物中苯的重量百分比＜0.0002%。
由本发明得到的粒状苯乙烯聚合物与使用过氧化苯甲酸特丁酯的常规聚合法制得的相比，事实上具有更低的残余单体含量。关于这一点最明显的例子就是在不改变聚合过程的周期条件下，用过氧碳酸2-乙己特戊酯和2，2-双（叔丁基过氧）丁烷能制得残余单体的重量百分比＜0.04%的产品。
本发明涉及一种在悬浮液体中用苯乙烯聚合法生产粒状可发性苯乙烯聚合物的工艺方法。即在80℃到130℃下在常规的悬浮稳定剂存在下加入重量百分比为3～15%的C3-C6碳氢化合物作为液体发泡剂。在本发明方法中用重量百分比为0.15-0.5%的过氧化二苯甲酰或有相近半衰期的过氧化物（可举的例子是过氧化二月桂酰和偶氮异丁腈）作为能产生自由基的聚合引发剂以及用重量百分比为0.05-0.6%，最好是0.1-0.4%的前面提到的过氧化物之一作为能在较高温度下分解的过氧化物。
在本发明中说的苯乙烯聚合物是指至少含有重量百分比为50%的苯乙烯的聚苯乙烯及其共聚物。譬如，适宜的共聚单体可以是α-甲基苯乙烯、在苯核上卤代的苯乙烯、丙烯腈、丙烯酸的酯类和甲基丙烯酸酯，其中的醇含1到8个碳原子，还有N-乙烯基化合物，譬如说，N-乙烯基咪唑。
可发性苯乙烯聚合物含有重量比为3-15%最好是5-8%的仅用于膨胀的已知C3-C6碳氢化合物，如丙烷，丁烷，异丁烷，正戊烷，1-戊烷，新戊烷，己烷和环己烷或它们的混合物，以用作液体发泡剂。
使用的基浮稳定剂，其一般常见的方式可以是有机防护胶体，如聚乙烯醇，聚乙烯吡咯烷酮和羟乙基纤维素;也可以是水不溶性分散剂，如细碎的磷酸三钙，氧化镁和磷酸钡;有机防护胶体和水不溶性分散溶剂的混合物也同样适用。
这种苯乙烯聚合物也可以含有有效剂量的其它常规添加剂，从而给可发泡产物带来特殊的性质。可举的例子有耐火剂，如四溴环辛烷，六溴环十二烷和溴代聚丁二烯，也可以是耐火剂的增效剂，如过氧化异丙苯，和其它在373K时的半衰期至少是2小时的能产生自由基的物质。
可发性苯乙烯聚合物也可以含有添加剂，如染料和填料，还有稳定剂。
实施例：
首先将240kg的水，400g的羟乙基纤维素，800g的磷酸三钙，和24g的EDTA作为悬浮介质加入6001的反应器中。此外再把在240g苯乙烯中加有960g过氧化二苯甲酰和480g过氧碳酸2-乙基己基特丁酯的溶液作为有机相加入。
将混合物在1小时内加热至90℃，并不断搅拌，恒温3.5小时。然后在1小时内计量加入120g的聚乙烯醇和20.4kg的戊烷，同时加热至110℃予以后稳定。再经过6.5小时的聚合时间后，经冷却和用吸滤器过滤，然后用水洗涤得到粒状聚合物，干燥过筛。
产量  253kg
K值  53.9
苯乙烯单体  385kg
苯  4.7mg/kg
液体发泡剂含量  重量比为6.18%
水含量  重量比为0.09%

Claims (5)

1、以液体悬浮法在两个不同温度段生产珠状可发生性苯乙烯均聚物或共聚物的非连续工艺方法，其特征在于第二温度段中使用的引发剂是一种脂肪族或者环状脂肪族的过酮缩醇或者过氧化一碳酸酯。
2、权利要求1的方法，其特征在于：使用的过酮缩醇是2，2-双（叔丁基过氧）丁烷，或1，1-双（叔丁基过氧）环己烷。
3、权利要求1的方法，其特征在于：使用的过氧化-碳酸酯是过氧化碳酸2-乙己戊酯或过氧化碳酸2-乙己叔丁酯。
4、权利要求1的方法，其特征在于：使用的过氧化二苯甲酰用在第一温度段。
5、权利要求1的方法，其特征在于：聚合的第一温度段是80℃90℃，第二温度段是105℃-130℃。
CN93106865A 1992-06-13 1993-06-11 珠状可发性苯乙烯聚合物的生产方法 Pending CN1080293A (zh)

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DEP4219379.6 1992-06-13
DE4219379A DE4219379A1 (de) 1992-06-13 1992-06-13 Verfahren zur Herstellung von perlförmigen expandierbaren Styrolpolymerisaten

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EP (1) EP0574665B1 (zh)
JP (1) JP2659506B2 (zh)
KR (1) KR0138974B1 (zh)
CN (1) CN1080293A (zh)
AT (1) ATE138946T1 (zh)
BR (1) BR9302291A (zh)
CA (1) CA2098240A1 (zh)
DE (2) DE4219379A1 (zh)
ES (1) ES2088187T3 (zh)
FI (1) FI932631A (zh)
MX (1) MX9303462A (zh)
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DE19749570A1 (de) * 1997-11-10 1999-05-12 Basf Ag Verfahren zur Herstellung von expandierbaren Styrolpolymerisaten
WO1999054391A1 (en) * 1998-04-17 1999-10-28 Nova Chemicals (International) S.A. Process for the preparation of expandable polymer particles
DE19835495A1 (de) * 1998-08-06 2000-02-10 Basf Ag Verfahren zur Herstellung von expandierbaren Styrolpolymerisaten
EP1251143B1 (en) * 2001-04-17 2012-07-18 Total Petrochemicals Research Feluy Monovinylaromatic polymer with improved stress crack resistance
US6608150B1 (en) * 2002-10-08 2003-08-19 Atofina Chemicals, Inc. Preparation of expandable styrene polymers
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US20080200573A1 (en) * 2005-08-08 2008-08-21 Albemarle Corporation Flame Retarded Styrenic Foams and Foam Precursors
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JP2659506B2 (ja) 1997-09-30
CA2098240A1 (en) 1993-12-14
DE4219379A1 (de) 1993-12-16
KR0138974B1 (ko) 1998-05-01
DE59302797D1 (de) 1996-07-11
ES2088187T3 (es) 1996-08-01
BR9302291A (pt) 1994-01-11
FI932631A (fi) 1993-12-14
TW284775B (zh) 1996-09-01
EP0574665B1 (de) 1996-06-05
NO300896B1 (no) 1997-08-11
NO932193L (no) 1993-12-14
NO932193D0 (no) 1993-06-14
MX9303462A (es) 1994-01-31
FI932631A0 (fi) 1993-06-09
KR940000486A (ko) 1994-01-03
ATE138946T1 (de) 1996-06-15
US5266603A (en) 1993-11-30
EP0574665A1 (de) 1993-12-22

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