CN1206393A - 抑制含烯键不饱和单体的聚合作用的方法 - Google Patents

抑制含烯键不饱和单体的聚合作用的方法 Download PDF

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CN1206393A
CN1206393A CN97191466A CN97191466A CN1206393A CN 1206393 A CN1206393 A CN 1206393A CN 97191466 A CN97191466 A CN 97191466A CN 97191466 A CN97191466 A CN 97191466A CN 1206393 A CN1206393 A CN 1206393A
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dihydroxycinnamic acid
acid
unsaturated monomer
ethylene linkage
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CN1076722C (zh
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格拉谢拉·B·阿汉西特
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Suez WTS USA Inc
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BetzDearborn Inc
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    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
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    • C07—ORGANIC CHEMISTRY
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

通过加入二羟基肉桂酸或其衍生物抑制含烯键不饱和单体例如异戊二烯和丁二烯在贮存或处理过程中的聚合作用。

Description

抑制含烯键不饱和单体的聚合作用的方法
技术领域
本发明涉及抑制含烯键不饱和单体的聚合作用的方法。该方法在氧气存在的贮存条件下对这些单体的聚合作用的抑制特别有效。背景技术
众所周知在加热时含烯键不饱和单体很容易聚合，并且聚合速率随温度升高而增加。由于该原因，通过加入用作聚合反应的抑制剂或阻滞剂，或者阻断引起(自由)基团形成的引发机理的物质来稳定所述单体。
某些含烯键不饱和(二烯烃)单体例如丁二烯及异戊二烯在低至室温下置于贮罐中或运输过程中即会进行聚合。该聚合作用是由含单体的系统中存在的氧气与二烯烃单体的反应所引发的。该反应产生了可进一步与二烯烃单体进行反应的过氧化物和自由基物质。
为了防止这类聚合反应的进行，二烯烃单体的生产商通常加入叔丁基邻苯二酚(TBC)作为聚合抑制剂。但是，TBC是一种有毒化合物，因而当它接触皮肤时会引起组织损伤，这些特征使得人们想去使用这样一种抑制剂，它既能克服这些困难，同时又能进行水和碱的提取以便在使用或进一步处理前能被很容易地从最终产品中除去。
本发明人发现二羟基肉桂酸及其衍生物能有效抑制含烯键不饱和单体在贮存和运输中的聚合作用。这些化合物在氧气存在下和高达100℃的温度下特别有效。
EP89-402156公开了一种含有基于稳定的抗坏血酸酯的抗氧化剂系统的化妆品制剂。抗氧化剂系统还含有生育酚或生育酚的混合物，二羟肉桂酸或其衍生物，配位剂以及非硫羟多肽。
日本公开JP59015477描述了一种对油和脂肪有效的食品抗氧化剂组合物，该组合物含有3，4-二羟基肉桂酸酯以及一种或多种抗坏血酸-硬脂酸酯，柠檬酸，苹果酸，以及抗坏血酸。本发明公开
本发明涉及抑制含烯键不饱和单体的聚合作用的方法，包括加入有效抑制量的二羟基肉桂酸或其衍生物。
本发明的二羟基肉桂酸或其衍生物具有下列通式：其中，R是H，CH3或C2H5；R1是H，CH3或C2H5，条件是至少一个R1是H。用于本发明的优选的化合物是二羟基肉桂酸及二羟基二氢肉桂酸。
含烯键不饱和单体的特征是可聚合的含烯键的不饱和烃，并且包括烯烃例如含2至20个碳原子并且优选含2至8个碳原子的α烯烃，以及共轭二烯烃，优选那些含4至6个碳原子的共轭二烯烃，例如异戊二烯和丁二烯。
在本发明中，术语“有效量”指的是抑制含烯键不饱和单体的聚合作用的必需的二羟基肉桂酸或其衍生物的量。根据含烯键不饱和单体在贮存和/或处理时所经历的条件，该量会有所变化。在较高的温度下和有较高量杂质的单体中，通常需要较大量的聚合作用抑制化合物。
加入含烯键不饱和单体中的有效量的二羟基肉桂酸或其衍生物的范围对于每百万份单体优选约为1份至1000份。更优选地，加入单体中的二羟基肉桂酸或其衍生物的量对于每百万份单体约为10份至200份。
当用于本发明的方法时，二羟基肉桂酸衍生物可与二羟基肉桂酸结合使用，或以二羟基肉桂酸衍生物的混合物进行使用。
通过使用适当的液体载体或溶剂可将二羟基肉桂酸或其衍生物以分散体或溶液的形式加入到含烯键不饱和单体中。任何可与二羟基肉桂酸或其衍生物以及含烯键不饱和单体相容的溶剂都可以使用。
本发明还提供一种包含异戊二烯及二羟基肉桂酸或其衍生物的组合物，所述二羟基肉桂酸或其衍生物含量范围为每百万份异戊二烯约1份至1000份，其具有如前述通式，其中R是H、CH3或C2H5；R1是H、CH3或C2H5，条件是至少一个R1是H。
本发明的组合物中，其中的二羟基肉桂酸或其衍生物选自二羟基肉桂酸和二羟基二氢肉桂酸。实施本发明的方式
现在通过参照几个特定的实例对本发明进行描述，这些实施例仅用作说明，并不作为对本发明范围的限制。实施例
进行试验以确定本发明抑制含烯键不饱和单体的聚合作用的有效性。
试验在不锈钢压力容器中进行，所述压力容器配备有玻璃样品容器及套子，塞子，带有连续记录仪的压力表，以及适当的阀和接头。将溶于40ml庚烷中的10ml的异戊二烯以及所指定的处理物加入到玻璃样品容器中并且置于压力容器内。关闭容器，注入100psig的氧气并且用100℃的水浴进行加热。连续记录压力直至到达压力-时间曲线的折点(即，曲线最大斜度)。引发时间计为将容器放到水浴中到到达折点之间的时间。测试结果列于表1中。
                 表1
聚合作用抑制试验
处理物    剂量(ppm)    引发时间(分钟)
 空白         -             25
 TBC          10            40
 BHT          10            31
              40            32
DHHCA         10            85
              25           144
 空白          -          21
 TBC          40          90
DHHCA         40          110
 DHCA         40          54
 空白          -          25
 DHCA         50          102
              100         127
TBC是叔丁基邻苯二酚
BHT是2，6-二-叔丁基-4-甲基苯酚
DHCA是3，5-二羟基肉桂酸
DHHCA是3，4-二羟基二氢肉桂酸
这些结果表明在接近于贮存的条件下本发明能有效抑制含烯键不饱和单体的聚合作用。已证明市售的抑制剂，TBC和BHT不如本发明化合物有效。工业实用性
二羟基肉桂酸或其衍生物能有效抑制贮存过程中或运输条件下的含烯键不饱和单体的聚合作用。人们发现所述的条件一般具有含氧的环境并且单体的温度可达100℃。本发明方法能抑制含烯键不饱和单体在处理过程中的聚合作用。这些处理条件，例如纯化和蒸馏处理，一般要加热而会常常引起单体的秽臭。
虽然本发明是通过特定的实施方案进行描述的，很显然本发明的其它的形式和修饰对于本领域的技术人员而言是显而易见的。所附权利要求和本发明应该被理解为覆盖了全部此类显而易见的形式和修饰，它们都属于本发明的精神和范围。

Claims (10)

1.抑制含烯键不饱和单体的聚合作用的方法，所述方法包括向单体中加入有效聚合作用抑制量的二羟基肉桂酸或其衍生物。
2.按照权利要求1所述的方法，其中所述的二羟基肉桂酸或其衍生物具有通式：
其中R是H，CH3或C2H5；R1是H，CH3或C2H5，条件是至少一个R1是H。
3.按照权利要求2的方法，其中所述的二羟基肉桂酸或其衍生物选自二羟基肉桂酸和二羟基二氢肉桂酸。
4.按照权利要求1的方法，其中所述二羟基肉桂酸或其衍生物加入所述单体的量的范围为每百万份单体约1份至约1000份。
5.按照权利要求1的方法，其中所述的含烯键不饱和单体选自异戊二烯和丁二烯。
6.按照权利要求1的方法，其中所述的单体暴露在有氧环境中。
7.按照权利要求1的方法，其中所述的单体具有的温度范围为从室温至约100℃。
8.含有含烯键不饱和单体及二羟基肉桂酸或其衍生物的组合物。
9.按照权利要求8的组合物，其中所述的含烯键不饱和单体选自异戊二烯和丁二烯。
10.按照权利要求8的组合物，其中所述的二羟基肉桂酸或其衍生物选自二羟基肉桂酸和二羟基二氢肉桂酸。
CN97191466A 1996-05-03 1997-04-04 抑制含烯键不饱和单体的聚合作用的方法 Expired - Fee Related CN1076722C (zh)

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DE (1) DE69716419T2 (zh)
ES (1) ES2180984T3 (zh)
MY (1) MY119143A (zh)
PT (1) PT900182E (zh)
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US5756870A (en) * 1996-05-03 1998-05-26 Betzdearborn Inc. Methods for inhibiting the polymerization of ethylenically unsaturated monomers
US6447649B1 (en) 2000-07-24 2002-09-10 Ge Betz, Inc. Polymerization inhibitor for vinyl-containing materials

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2388041A (en) * 1941-07-26 1945-10-30 Goodrich Co B F Process for the extraction of butadiene
US2473203A (en) * 1946-02-26 1949-06-14 Standard Oil Dev Co Diolefin distillation
US3510405A (en) * 1967-11-11 1970-05-05 Nippon Zeon Co Isoprene purification process
EG10435A (en) * 1971-03-03 1976-01-31 Snam Progetti Method for inhibiting the polymerization of conjugated dienes
CA961863A (en) * 1971-07-28 1975-01-28 Alexandr G. Liakumovich Method of inhibiting the thermopolymerization of isoprene and butadiene
US3951754A (en) * 1974-02-19 1976-04-20 Liakumovich Alexandr Grigoriev Method of inhibiting the thermopolymerization of isoprene and butadiene
US4439278A (en) * 1982-06-21 1984-03-27 Eastman Kodak Company Process inhibitor for readily polymerizable ethylenically unsaturated aromatic compounds
SU1098200A1 (ru) * 1982-07-06 1986-05-07 Предприятие П/Я Р-6913 Ингибитор самопроизвольной полимеризации изопрена
JPS5915477A (ja) * 1982-07-16 1984-01-26 Tanabe Seiyaku Co Ltd 抗酸化剤
US4596655A (en) * 1983-08-17 1986-06-24 The Dow Chemical Company Process for separating an ethylenically unsaturated hydrocarbon from a hydrocarbon mixture
IL76434A0 (en) * 1985-09-20 1986-01-31 Bromine Compounds Ltd Flame retardant polymer compositions
US4725628A (en) * 1986-07-18 1988-02-16 Kimberly-Clark Corporation Process of making a crosslinked superabsorbent polyurethane foam
FR2635019B1 (fr) * 1988-08-02 1992-06-12 Centre Nat Rech Scient Materiau capable de fixer les substances biologiques, et ses applications notamment comme support de chromatographie d'affinite
US5043504A (en) * 1990-09-05 1991-08-27 The Dow Chemical Company Inhibition of butadiene-polymerization during the conversion of butadiene to vinylcyclohexene
US5221498A (en) * 1991-07-22 1993-06-22 Betz Laboratories, Inc. Methods and compositions for inhibitoring polymerization of vinyl monomers
US5416258A (en) * 1994-01-14 1995-05-16 Betz Laboratories, Inc. Methods for inhibiting ethylenically unsaturated monomers
US5396005A (en) * 1994-01-19 1995-03-07 Betz Laboratories, Inc. Compositions and methods for inhibiting polymerization of ethlenically unsaturated monomers
US5756870A (en) * 1996-05-03 1998-05-26 Betzdearborn Inc. Methods for inhibiting the polymerization of ethylenically unsaturated monomers

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US5756870A (en) 1998-05-26
EP0900182A1 (en) 1999-03-10
DE69716419D1 (de) 2002-11-21
ES2180984T3 (es) 2003-02-16
PT900182E (pt) 2002-12-31
US5886241A (en) 1999-03-23
EP0900182B1 (en) 2002-10-16
CN1076722C (zh) 2001-12-26
WO1997042146A1 (en) 1997-11-13
AR006268A1 (es) 1999-08-11
DE69716419T2 (de) 2003-07-10
MY119143A (en) 2005-04-30
ZA97966B (en) 1997-08-18
BR9708897A (pt) 1999-08-03

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