CN1944418A - 含有苯乙烯官能团的氧杂环丁烷化合物 - Google Patents
含有苯乙烯官能团的氧杂环丁烷化合物 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
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- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
这些化合物含有氧杂环丁烷官能团和苯乙烯官能团。氧杂环丁烷官能团可以在反应中均聚,它能进行阳离子或阴离子开环,并且苯乙烯官能团可以与诸如电子受体化合物的化合物聚合。这种双官能团使得可以进行两种固化处理。所述化合物具有下述结构,其中R1是甲基或乙基;R2和R3是H或甲基或乙基;R4是直接的键或二价烃;X和Y独立地是直接的键,或醚、酯、酰胺或氨基甲酸酯基,条件是X和Y两者不都是直接的键;Q是二价烃(其可以含有N、O或S杂原子);和G是-OR1、-SR1、或-N(R2)(R3),其中R1、R2和R3如上所述。
Description
本申请是分案申请,其母案申请是申请日为2004年4月21日、申请号为200480000440.1、发明名称为“含有苯乙烯官能团的氧杂环丁烷化合物”的申请。
技术领域
本发明涉及含有苯乙烯官能团的氧杂环丁烷化合物。
背景技术
氧杂环丁烷是具有高反应活性的环醚,它能进行阳离子和阴离子开环均聚反应。苯乙烯化合物能够进行自由基聚合反应。
发明概述
本发明涉及含有氧杂环丁烷官能团和苯乙烯官能团的化合物。这些化合物可以在反应中均聚,在反应中氧杂环丁烷能进行阳离子或阴离子开环,或者这些化合物可以与诸如电子受体化合物的化合物聚合。这种双官能团使得可以进行两种固化处理-热固化或辐射固化。这种能力使得上述化合物在许多应用中是引人注意的,比如作为粘合剂、涂料、密封剂和复合材料。
发明详述
在一个实施方案中,本发明的化合物可由下式表示:
其中R1是甲基或乙基;R2和R3是H或甲基或乙基;R4是直接的键或二价烃;X和Y独立地是直接的键,条件是两者不都是直接的键,或者是醚、酯、酰胺或氨基甲酸酯基;Q是二价烃(其可以含有N、O或S杂原子);和G是-OR1、-SR1、或-N(R2)(R3),其中R1、R2和R3如上所述;条件是当R4、Q和Y不存在,且R2和R3是H时,X不是
并且条件是当R4是Q和Y不存在,且R2和R3是H时,X不是-O-。Q位置的构型取决于起始苯乙烯化合物的构型。
所述起始苯乙烯化合物可以是小分子,例如3-异丙烯基-α,α-二甲基-苄基异氰酸酯(m-TMI)、4-乙烯基-苄基氯、m-TMI与二醇的反应产物、m-TMI与含有羟基的羧酸中的羟基官能团反应的产物和异丁子香酚。所述起始苯乙烯化合物还可以是低聚物或聚合物,例如通过m-TMI或4-乙烯基-苄基氯与双官能团的低聚物或聚合物中的一个官能团反应而制得。
无论所述起始苯乙烯化合物是小分子还是低聚物或聚合物,其含有由下述结构式表示的苯乙烯官能团:
其中R2和R3是H或甲基或乙基和G是-OR1、-SR1、或-N(R2)(R3),其中R1是甲基或乙基且R2和R3独立地是H或甲基或乙基。所述起始苯乙烯化合物还含有可与起始氧杂环丁烷化合物反应的第二种官能团。例如,上述公开的苯乙烯起始物质除了含有苯乙烯官能团之外,还含有卤素、羟基、或异氰酸酯官能团。
所述起始氧杂环丁烷化合物可以是小分子或低聚或聚合分子,例如其通过下述公开的小分子氧杂环丁烷起始化合物中的一种与双官能团的低聚物或聚合物中的一个官能团反应而制得。无论哪种情况,所述起始氧杂环丁烷化合物含有由下述结构表示的氧杂环丁烷官能团:
以及可与苯乙烯起始化合物中的第二种官能团反应的第二种官能团。
适宜的起始氧杂环丁烷化合物是小分子,例如包括
(a)醇,比如3-甲基-3-羟甲基氧杂环丁烷,3-乙基-3-羟甲基氧杂环丁烷;
(b)卤化物,比如3-甲基-3-溴甲基氧杂环丁烷,3-乙基-3-溴甲基氧杂环丁烷,其可以通过本领域已知的来自(a)的醇与CBr4的反应而制得;
(c)烷基卤化物,比如3-甲基-3-烷基溴甲基氧杂环丁烷,3-乙基-3-烷基溴甲基氧杂环丁烷,其可以通过本领域已知的二溴代烷基化合物与来自(a)的氧杂环丁烷醇的反应而制得;
和(d)甲苯磺酸酯,比如3-甲基-3-甲苯磺酰基甲基氧杂环丁烷,3-乙基-3-甲苯磺酰基甲基氧杂环丁烷,其可以由对甲苯磺酰氯制备:
当需要含有苯乙烯和氧杂环丁烷的较长链和较高分子量化合物时,起始苯乙烯化合物或者起始氧杂环丁烷或者两者均可以通过与双官能团的低聚物或聚合物反应而延伸。如果在苯乙烯起始化合物和双官能团的低聚物或聚合物之间进行第一种反应,那么该低聚物或聚合物中的第二种官能团必定可与氧杂环丁烷起始化合物反应,并且如果氧杂环丁烷起始化合物和双官能团的低聚物或聚合物之间进行第一种反应,那么该低聚物或聚合物中的第二种官能团必定可与苯乙烯起始化合物反应。
适宜的并且可以商业获得的低聚物和聚合物的例子包括二聚二醇和具有末端羟基官能团的聚(丁二烯)。
在氧杂环丁烷和苯乙烯化合物均通过与双官能团的低聚物或聚合物反应而延伸的情况下,Q还可以含有例如醚、酯、氨基甲酸酯、或脲官能团的官能团,其是由两个低聚或聚合起始物质反应而得。
通常,含有氧杂环丁烷和苯乙烯官能团的本发明化合物的制备是由含有氧杂环丁烷官能团和第二种官能团的起始化合物与含有苯乙烯官能团和可与氧杂环丁烷化合物中的第二种官能团反应的第二种官能团的起始化合物一起反应。通常的反应流程包括众所周知的加成、取代和缩合反应。
在另一个实施方案中,本发明化合物包括聚合物,其含有一个以上氧杂环丁烷官能团和一个以上苯乙烯官能团。上述化合物是由聚合起始化合物制备的,在该聚合起始化合物上悬挂着可与起始氧杂环丁烷化合物和起始苯乙烯化合物反应的官能团。
所述聚合物具有下述结构:
结构式中polymer为聚合物
其中聚合物是聚合骨架,其上悬挂着氧杂环丁烷和苯乙烯官能团;m和n是整数,其会随着由实验者添加的氧杂环丁烷和苯乙烯官能团的水平而改变,并且通常为2-500;R1是甲基或乙基;R2和R3独立地是H或甲基或乙基;R4是直接的键或二价烃;W和Z独立地是醚、酯、酰胺或氨基甲酸酯基(通过聚合物下垂的官能团分别与起始氧杂环丁烷或起始苯乙烯化合物上相应的反应官能团反应而形成);和G是-OR1、-SR1、或-N(R2)(R3),其中R1、R2和R3如上所述。
聚合物下垂的官能团可以通过烃(例如具有1-20个碳原子)与聚合骨架相连,所述烃本身悬挂在聚合骨架上。为了说明,这些悬挂的基团被认为是聚合骨架的一部分。
商业可获得的且适宜的聚合骨架的例子是具有下垂羟基基团的聚(丁二烯)。所述下垂的羟基可与含有甲苯磺酰离去基的氧杂环丁烷起始化合物以及m-TMI反应。在这种情况下,连接基W是醚官能团且Z含有氨基甲酸酯官能团。
作为另一个例子,具有下垂的羧酸官能团的聚(丁二烯)可与羟基氧杂环丁烷起始化合物上的羟基官能团反应以及与m-TMI上的异氰酸酯官能团反应。在这种情况下,W基团是酯官能团且Z含有氨基甲酸酯官能团。
聚合起始物质可以商业购买,例如从Zeon Chemicals获得丙烯腈-丁二烯橡胶和从Johnson Polymer获得苯乙烯-丙烯酸共聚物。上述聚合物下垂的官能团是羟基或羧酸官能团。
其它起始聚合物质可以利用本领域熟练技术人员已知的标准聚合技术由丙烯酸和/或乙烯单体合成而得。适宜的丙烯酸单体包括具有3-5个碳原子的α,β-不饱和一元和二元羧酸以及丙烯酸酯单体(丙烯酸和甲基丙烯酸的烷基酯,其中烷基含有1-14个碳原子)。例子是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正辛酯、甲基丙烯酸正壬酯,及其相应的分支异构体,比如2-乙基己基丙烯酸酯。适宜的乙烯单体包括乙烯酯、乙烯醚、卤化乙烯、亚乙烯基二卤化物,以及烯键式不饱和烃的腈。例子是乙酸乙烯酯、丙烯酰胺、1-辛基丙烯酰胺、丙烯酸、乙烯基乙醚、氯乙烯、亚乙烯基二氯化物、丙烯腈、马来酸酐,和苯乙烯。
其它聚合起始物质可以利用本领域熟练技术人员已知的标准聚合技术由共轭的二烯和/或乙烯单体制得。适宜的共轭二烯单体包括丁二烯-1,3,2-氯丁二烯-1,3,异戊二烯,间戊二稀和共轭的己二烯。适宜的乙烯单体包括苯乙烯、α-甲基苯乙烯、二乙烯基苯、氯乙烯、乙酸乙烯酯、亚乙烯基二氯化物、甲基丙烯酸甲酯、丙烯酸乙酯、乙烯基吡啶、丙烯腈、甲基丙烯腈、甲基丙烯酸、衣康酸和丙烯酸。
本领域熟练技术人员具有足够的专业技能去选择上述单体合适的组合以及随后的反应,得以能够添加下垂的官能团例如羟基和羧基官能团,其用于添加本说明书中公开的氧杂环丁烷和苯乙烯官能团。
实施例
实施例1:制备苯乙烯氨基甲酸乙基氧杂环丁烷酯
将3-乙基-3-羟甲基-氧杂环丁烷(40.00g,0.3442mol)和m-TMI(69.43g,0.3442mol)混合于250ml的四颈圆底烧瓶中,该烧瓶装备了冷凝器、机械混合器、氮气排空和油浴。在氮气下,搅拌并在油浴中加热到65℃进行反应。加入一滴二月桂酸二丁锡,从而引起放热反应,最高达125℃。移去油浴并且在15分钟内反应温度降到65℃。这时根据在2254cm-1处FT-IR的异氰酸酯峰的消失确定反应完成。然后从烧瓶中的移出产物,其为粘稠且无色的液体;但是,过一会其结晶为白色固体,熔点为52℃。
H1-NMR:δ7.21-7.61(m,4H),5.45(s,1H),5.23(bs,1H),5.12(s,1H),4.61-4.21(bm,3H),4.05(s,3H),2.15(s,3H),1.55-1.85(bm,8H),0.55-1.01(bm,3H).
实施例2:制备苯乙烯氨基甲酸甲基氧杂环丁烷酯
将3-甲基-3-氧杂环丁烷甲醇(20.00g,0.1958mol)和m-TMI(39.49g,0.1958mol)混合于250ml的四颈圆底烧瓶中,该烧瓶装备了冷凝器、机械混合器、温度计、氮气排空和油浴。在氮气下,搅拌并在油浴中加热到65℃进行反应。加入一滴二月桂酸二丁锡,并且在5小时内根据FT-IR的异氰酸酯峰(2254cm-1)的消失确定反应完成。然后从烧瓶中的移出产物,其为无色液体,粘度为21,000cPs。
H1-NMR:δ7.61(s,1H),7.42(s,3H),5.45(s,1H),5.31(bs,1H),5.15(s,1H),4.61(bm,1H),4.39(bm,1H),4.12(s,4H),2.21(s,3H),1.72(bs,6H),0.95-1.35(bm,3H).
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