CN110546178A - 接枝聚合物的制造方法、接枝聚合物、接枝聚合物的引发剂 - Google Patents
接枝聚合物的制造方法、接枝聚合物、接枝聚合物的引发剂 Download PDFInfo
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- CN110546178A CN110546178A CN201880014950.6A CN201880014950A CN110546178A CN 110546178 A CN110546178 A CN 110546178A CN 201880014950 A CN201880014950 A CN 201880014950A CN 110546178 A CN110546178 A CN 110546178A
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- radical polymerization
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- 239000003054 catalyst Substances 0.000 claims abstract description 17
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- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
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- 150000003624 transition metals Chemical class 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical group [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 1
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- 229940046009 vitamin E Drugs 0.000 description 1
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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Abstract
[课题]本发明提供一种接枝聚合物的制造方法,该制造方法通过使用含有碘引发基团的单体结构单元作为引发剂,能够更稳定地进行活性自由基聚合。[解决手段]该制造方法的特征在于,通过在有机催化剂的作用下使主链中具有下述式(1)所示的重复单元的化合物与乙烯基系单体进行活性自由基聚合而制造接枝聚合物。[化学式14]此处,R1:连接基团(可以包含醚键、酰胺键或酯键的碳原子数为1~30的直链状、支链状或环状的亚烷基、芳香族基团);R2、R3、R4、R5、R6:氢原子、芳香族基团、脂肪族基团;n=1~5。
Description
技术领域
本发明涉及一种接枝聚合物的制造方法、利用该制造方法制造的接枝聚合物以及接枝聚合物的引发剂,该接枝聚合物的制造方法用于通过对由含有碘引发基团的单体结构单元构成的引发剂使用廉价且稳定的有机催化剂而容易地进行活性自由基聚合、制造接枝聚合物。
背景技术
近年来,正在基于高分子结构的精密控制而进行各种高功能性材料的开发。其中,通过利用自由基聚合的高反应性,已能够实现多种多样的乙烯基系单体的聚合,还能够实现更具创新性的功能性材料的开发。
在该自由基聚合中,特别是活性自由基聚合是从稳定的共价键种可逆地生成自由基种的聚合反应。活性自由基聚合过程仅由引发反应和生长反应构成,由于不伴有链转移反应,因而可得到长度各自统一的聚合物,而且由于不伴有使引发剂的生长末端失活的副反应,因而其生长末端在聚合中持续生长,能够制作出仿佛有生命的聚合物。即,该活性自由基聚合兼具活性聚合和自由基聚合各自的优异特性,能够用于具有更高功能的高分子材料的开发。
另外,在这种活性自由基聚合中,作为过渡金属催化剂、自由基引发剂,有时不得不使用危险且难以合成的过氧化物。因此,为了使活性自由基聚合安全且容易地进行,对于以重复单元为主链的作为引发剂的聚合物,需要使其接触廉价且稳定的有机催化剂。
以往,作为使以具有引发基团的化学结构作为重复单元的聚合物进行活性自由基聚合的技术,例如公开了专利文献1、2中记载的技术。
现有技术文献
专利文献
专利文献1:日本特开2004-18556号公报
专利文献2:日本特开2014-117672号公报
发明内容
发明所要解决的课题
在通过进行该活性自由基聚合而制造接枝聚合物时,特别要求更稳定地进行活性自由基聚合。虽然理论上可以预测,通过使用含有碘引发基团的单体结构单元,能够更稳定地进行活性自由基聚合,但现状是,在上述专利文献1、2的公开技术中,并未特别公开使用以含有碘引发基团的单体结构单元作为重复单元的聚合物作为引发剂的技术,并且在专利文献1、2的公开技术以外的公开中也未特别得到验证。
因此,本发明是鉴于上述问题而想出的,其目的在于提供一种接枝聚合物的制造方法、利用该制造方法制造的接枝聚合物以及接枝聚合物的引发剂,该接枝聚合物的制造方法通过使用含有碘引发基团的单体结构单元作为引发剂,能够更稳定地进行活性自由基聚合。
用于解决课题的手段
本发明人为了使用含有碘引发基团的单体结构单元作为引发剂来进行活性自由基聚合,进行了深入研究。结果发现,通过使用主链中具有下述式(1)所示的重复单元的化合物作为引发剂,能够更稳定地进行活性自由基聚合而制造接枝聚合物。
即,第1发明的接枝聚合物的制造方法的特征在于,通过在有机催化剂的作用下使主链中具有下述式(1)所示的重复单元的化合物与乙烯基系单体进行活性自由基聚合而制造接枝聚合物。
[化学式1]
此处,R1:连接基团(可以包含醚键、酰胺键或酯键的碳原子数为1~30的直链状、支链状或环状的亚烷基、芳香族基团)
R2、R3、R4、R5、R6:氢原子、芳香族基团、脂肪族基团
n=1~5
另外,第2发明的接枝聚合物的制造方法的特征在于,在由胺化合物、膦化合物、膦酸酯化合物、鏻盐、碘化酰亚胺化合物或铵化合物中的任一种构成的有机催化剂的作用下,进行上述活性自由基聚合。
第3发明的接枝聚合物的特征在于,其是通过第1发明或第2发明所述的接枝聚合物的制造方法制造的。
第4发明的接枝聚合物的引发剂的特征在于,其作为第1发明或第2发明所述的接枝聚合物的制造方法中的与乙烯基系单体进行活性自由基聚合的引发剂来使用,其在主链中具有下述式(1)所示的重复单元。
[化学式2]
第5发明的接枝聚合物的引发剂的特征在于,其作为在有机催化剂的作用下与乙烯基系单体进行活性自由基聚合的引发剂来使用,其在主链中具有下述式(1)所示的重复单元。
[化学式3]
此处,R1:-COO-(CH2)aOCO-
R2、R3、R4、R5、R6:氢原子、脂肪族基团
a=2~5
发明的效果
根据包含上述构成的本发明,能够稳定地进行活性自由基聚合,进而能够稳定地制造接枝聚合物。
具体实施方式
下面,对本发明的实施方式的接枝聚合物的制造方法进行详细说明。
应用了本发明的接枝聚合物的制造方法中,在有机催化剂的作用下使主链中具有式(1)所示的重复单元的化合物与乙烯基系单体进行活性自由基聚合。
[化学式4]
此处,R1为连接基团。特别是,该R1是可以包含醚键、酰胺键或酯键的碳原子数为1~30的直链状、支链状或环状的亚烷基、芳香族基团。另外,R2、R3、R4、R5、R6为氢原子、芳香族基团、脂肪族基团等,n=1~5。
对于作为该引发剂的化合物而言,前提是具有碘引发基团的结构单元连续。
与这种式(1)所示的作为引发剂的化合物反应的乙烯基系单体(自由基聚合性单体)是指具有能够在有机自由基的存在下进行自由基聚合的不饱和键的单体。即,本发明的聚合方法中可以使用现有公知进行活性自由基聚合的任意的单体。
更具体而言,可以使用被称为所谓乙烯基系单体的单体。乙烯基系单体是通式(2)所示的单体的总称。
CHR7=CR8R9 (2)
(式中,R7、R8和R9分别表示氢原子或有机基团。)
需要说明的是,通式(1)所示的单体包括以下例示的单体。
作为乙烯基系单体,可以适当使用苯乙烯及其衍生物(R7和R8为氢原子、R9为具有或不具有取代基的苯基);丙烯酸(R7和R8为氢原子、R9为羧基);丙烯酰胺(R7和R8为氢原子、R9为-CONH2基团)及其衍生物;丙烯酸酯(丙烯酸酯或丙烯酸盐);甲基丙烯酸(R7为氢原子、R8为甲基、R9为羧基)(MAA);甲基丙烯酰胺(R7为氢原子、R8为甲基、R9为-CONH2基团)(MAAm)及其衍生物;甲基丙烯酸酯(甲基丙烯酸酯或甲基丙烯酸盐)。
作为苯乙烯及其衍生物的具体例,可以举出苯乙烯(St);邻甲氧基苯乙烯、间甲氧基苯乙烯或对甲氧基苯乙烯;邻叔丁氧基苯乙烯、间叔丁氧基苯乙烯或对叔丁氧基苯乙烯;邻氯甲基苯乙烯、间氯甲基苯乙烯或对氯甲基苯乙烯;邻氯苯乙烯、间氯苯乙烯或对氯苯乙烯;邻羟基苯乙烯、间羟基苯乙烯或对羟基苯乙烯;邻苯乙烯磺酸、间苯乙烯磺酸或对苯乙烯磺酸及其衍生物;邻苯乙烯磺酸钠、间苯乙烯磺酸钠或对苯乙烯磺酸钠;邻苯乙烯硼酸、间苯乙烯硼酸或对苯乙烯硼酸及其衍生物等。
作为丙烯酰胺及其衍生物的具体例,可以举出丙烯酰胺、N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-羟乙基丙烯酰胺等。
作为丙烯酸酯的具体例,可以举出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸己酯、丙烯酸-2-乙基己酯、丙烯酸正辛酯、丙烯酸壬酯、丙烯酸癸酯、丙烯酸月桂酯等丙烯酸烷基酯;丙烯酸苄酯等丙烯酸芳基烷基酯;丙烯酸四氢糠基酯;丙烯酸缩水甘油酯等丙烯酸环氧烷基酯;丙烯酸环己酯等丙烯酸环烷基酯;丙烯酸-2-甲氧基乙酯、丙烯酸丁氧基乙酯等丙烯酸烷氧基烷基酯;丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯等丙烯酸羟基烷基酯;二乙二醇丙烯酸酯、聚乙二醇丙烯酸酯等聚亚烷基二醇丙烯酸酯;甲氧基四乙二醇丙烯酸酯、甲氧基聚乙二醇丙烯酸酯等烷氧基聚亚烷基二醇丙烯酸酯;丙烯酸-2-(二甲氨基)乙酯等丙烯酸二烷基氨基烷基酯;丙烯酸-3-氯-2-羟基丙酯;丙烯酸-2-羟基-3-苯氧基丙酯等。也可以使用丙烯酸烷基酯的烷基上取代有氟原子的丙烯酸氟代烷基酯、丙烯酸烷基酯的烷基上取代有三(三烷基甲硅烷氧基)甲硅烷基的化合物。另外,可以使用2-(N,N-二乙基-N-甲基氨基)乙基丙烯酸酯+/三氟磺酰基亚胺(N(CF3SO2)2 -)盐、2-(N-乙基-N-甲基-N-氢化氨基)乙基丙烯酸酯+/三氟磺酰基亚胺(N(CF3SO2)2 -)盐、1-乙基-3-甲基咪唑鎓丙烯酸酯+/氟氢化((FH)nF-)盐等离子液体性的丙烯酸酯。
作为甲基丙烯酰胺及其衍生物的具体例,可以举出甲基丙烯酰胺(MAAm)、N-异丙基甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟乙基甲基丙烯酰胺等。
作为甲基丙烯酸酯的具体例,可以举出甲基丙烯酸甲酯(MMA)、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸正辛酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯(LMA)、甲基丙烯酸月桂酯等甲基丙烯酸烷基酯;甲基丙烯酸苄酯(BzMA)等甲基丙烯酸芳基烷基酯;甲基丙烯酸四氢糠基酯;甲基丙烯酸缩水甘油酯等甲基丙烯酸环氧烷基酯;甲基丙烯酸环己酯等甲基丙烯酸环烷基酯;甲基丙烯酸-2-甲氧基乙酯、甲基丙烯酸丁氧基乙酯等甲基丙烯酸烷氧基烷基酯;甲基丙烯酸-2-羟基乙酯(HEMA)、甲基丙烯酸-2-羟基丙酯、甘油单甲基丙烯酸酯等甲基丙烯酸羟基烷基酯;二乙二醇甲基丙烯酸酯、聚乙二醇甲基丙烯酸酯等聚亚烷基二醇甲基丙烯酸酯;甲氧基四乙二醇甲基丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯(PEGMA)等烷氧基聚亚烷基二醇甲基丙烯酸酯;甲基丙烯酸-2-(二甲氨基)乙酯(DMAEMA)等甲基丙烯酸二烷基氨基烷基酯;甲基丙烯酸-3-(三甲氧基甲硅烷基)丙酯等甲基丙烯酸烷氧基甲硅烷基烷基酯;甲基丙烯酸-3-氯-2-羟基丙酯;甲基丙烯酸-2-羟基-3-苯氧基丙酯等。也可以使用甲基丙烯酸烷基酯的烷基上取代有氟原子的甲基丙烯酸-2,2,3,4,4,4-六氟丁酯(HFBMA)等甲基丙烯酸氟代烷基酯、甲基丙烯酸烷基酯的烷基上取代有三(三烷基甲硅烷氧基)甲硅烷基的甲基丙烯酸-3-[[三(三甲基甲硅烷氧基)甲硅烷基]丙酯(MOPES)等化合物。另外,可以使用2-(N,N-二乙基-N-甲基氨基)乙基甲基丙烯酸酯+/三氟磺酰基亚胺(N(CF3SO2)2 -)盐、2-(N-乙基-N-甲基-N-氢化氨基)乙基甲基丙烯酸酯+/三氟磺酰基亚胺(N(CF3SO2)2 -)盐、1-乙基-3-甲基咪唑鎓甲基丙烯酸酯+/氟氢化((FH)nF-)盐、N-乙基-N-甲基吡咯烷鎓甲基丙烯酸酯+/氟氢化((FH)nF-)盐等离子液体性的甲基丙烯酸酯。
本发明中,在R8和R9均为羧基或具有羧酸酯的基团的情况下,反应也适当地进行。具体而言,可以举出衣康酸(ITA)、衣康酸二甲酯(Me2ITA)、衣康酸单丁酯(BuITA)等衣康酸、其单烷基酯和其二烷基酯。
本发明中,也可以使用具有2个以上双键(乙烯基、异丙烯基等)的单体。具体而言,例如为二烯系化合物(例如丁二烯、异戊二烯等)、具有2个烯丙基的化合物(例如邻苯二甲酸二烯丙酯等)、具有2个甲基丙烯酰基的化合物(例如乙二醇二甲基丙烯酸酯)、具有2个丙烯酰基的化合物(例如乙二醇二丙烯酸酯)等。
本发明中,也可以使用上述以外的乙烯基系单体。具体而言,例如为乙烯基酯类(例如乙酸乙烯酯、丙酸乙烯酯、苯甲酸乙烯酯、乙酸乙烯酯)、上述以外的苯乙烯衍生物(例如α-甲基苯乙烯)、乙烯基酮类(例如乙烯基甲基酮、乙烯基己基酮、甲基异丙烯基酮)、N-乙烯基化合物(例如N-乙烯基吡咯烷酮、N-乙烯基吡咯、N-乙烯基咔唑、N-乙烯基吲哚)、丙烯腈(AN)、甲基丙烯腈、马来酸及其衍生物(例如马来酸酐)、卤化乙烯类(例如氯乙烯、偏二氯乙烯、四氯乙烯、六氯丙烯、氟乙烯)、烯烃类(例如乙烯、丙烯、1-丁烯或2-丁烯、1-己烯、环己烯)等。
这些自由基聚合性单体可以单独使用,另外也可以合用两种以上。在使用两种以上的单体时,可以在反应开始时同时添加,或者也可以伴随聚合的进行而逐次添加。
作为有机催化剂的例子,为能够从碘化合物中攫取碘原子而产生碳自由基的化合物,大致分类包括有机磷化合物、有机氮化合物、有机氧化合物、有机硫化合物等。
有机磷化合物大致分类包括膦化合物、膦酸酯化合物、鏻盐、磷腈盐等。
作为膦化合物,为三乙基膦、三丁基膦、三苯基膦等;作为膦酸酯化合物,为甲基膦酸、乙基膦酸、苯基膦酸、甲基膦酸二甲酯、甲基膦酸二苯酯等;作为鏻盐,为甲基三丁基碘化鏻、四苯基碘化鏻等;作为磷腈盐,为六苯基二磷腈氯化物等;作为亚磷酸酯化合物,为亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二丁酯、亚磷酸二苯酯等。
有机氮化合物大致分类包括胺类、酰亚胺类、咪唑鎓盐类、吡啶鎓盐类、铵盐类、碘化胺类、碘化酰亚胺类等。
胺类为三乙胺、三丁胺、四(二甲氨基)乙烯、1,4,8,11-四甲基-1,4,8,11-四氮杂环十四烷、二苯基胺等。酰亚胺类为琥珀酰亚胺等。另外,咪唑鎓盐类为1-甲基-3-甲基-咪唑鎓碘化物、1-乙基-3-甲基咪唑鎓溴化物等。吡啶鎓盐类为2-氯-1-甲基吡啶鎓碘化物等。铵盐类为四丁基碘化铵、四丁基三碘化铵、四丁基溴二碘化铵等。碘化胺类为碘化二苯胺等。碘化酰亚胺类为碘化琥珀酰亚胺、碘化马来酰亚胺、碘化邻苯二甲酰亚胺、1,3-二碘-5,5-二甲基乙内酰脲等。
有机氧化合物大致分类包括苯酚类、醇类、呋喃类等。苯酚类为2,4,6-三甲基苯酚、2,6-二叔丁基-4-甲基苯酚、2,4-二甲基苯酚、2-异丙基-5-甲基苯酚、2,6-二叔丁基-4-甲氧基苯酚、2,6-二甲氧基-4-甲基苯酚、2,6-二甲基-4-氰基苯酚、4-硝基苯酚、苯酚、维生素E、对苯二酚、间苯二酚、邻苯二酚、4-叔丁基邻苯二酚、2-甲氧基对苯二酚、羟基对苯二酚等。醇类为苯甲醇、1-苯基乙醇、维生素C等。呋喃类为呋喃、低聚呋喃、聚呋喃等。
有机硫化合物大致分类包括噻吩类、锍盐类等。噻吩类为噻吩、低聚噻吩、聚噻吩等。锍盐类为三丁基碘化锍等。
上述活性自由基聚合反应例如可以由下述式(3)所示的化学式表示。
[化学式5]
m=2~10000
通过在有机催化剂的存在下使自由基聚合性聚合物与式(1)所示的引发剂反应,生成式(3)所示的接枝聚合物。
需要说明的是,生成的接枝聚合物的化学结构式也可以与上述式(3)中记载的结构不同。特别是,该生成的聚合物可以为均聚物,也可以为共聚物(共聚物、三元共聚物等)。另外,生成的共聚物可以为无规共聚物、嵌段共聚物中的任一种。
通过将这样的式(1)所示的化合物作为引发剂进行活性自由基聚合反应,能够更稳定地生成接枝聚合物。特别是,根据本发明,在活性自由基聚合中也无需再使用危险的过氧化物作为引发剂、催化剂,因而能够安全地进行反应。
需要说明的是,在使本发明的活性自由基聚合反应进行的方面,反应温度没有特别限定,但优选为0℃~180℃、更适宜优选为30℃~120℃。另外,该反应温度进一步适宜优选为40℃~80℃。另外,反应时间可以在30分钟~24小时的范围内适当选择适合各反应的时间。
另外,可以在无溶剂条件下进行本发明的活性自由基聚合反应,也可以使用溶剂。此时的反应溶剂只要不抑制反应即可,没有特别限制,可以使用任何溶剂。作为该反应溶剂的例子,可以直接使用在以往的活性自由基聚合中使用的溶剂。具体而言,例如可以使用水、乙醇等各种醇类、碳酸亚乙酯等碳酸酯类、乙酸丁酯等酯类、N,N-二甲基-2-甲氧基乙基酰胺(DMMEA)、二甲基甲酰胺(DMF)等酰胺类、二乙二醇二甲醚(diglyme)等醚类等。
另外,作为本发明的活性自由基聚合反应的反应条件,也可以在空气存在的条件下进行。另外,根据需要,也可以在氮气、氩气等非活性气氛下进行反应。
应用了本发明的接枝聚合物的制造方法中,也可以为下述方式:对于具有碘引发基团的结构单元连续而成的作为引发剂的碘化乙烯基系单体、自由基聚合性单体和有机催化剂的混合物,进一步加入其他引发剂来进行聚合反应。
该情况下,作为其他引发剂,可以使用在自由基反应中使用的公知的自由基引发剂。作为该公知的自由基引发剂的例子,可以举出偶氮系自由基引发剂、过氧化物系自由基引发剂等。作为偶氮系自由基引发剂的具体例,可以举出偶氮二(异丁腈)(AIBN)、2,2’-偶氮二(2,4-二甲基戊腈)(V65)、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)(V70)、2,2’-偶氮二(2-甲基丙酸)二甲酯(V601)、2,2’-偶氮二(2-甲基丁腈)(V59)、1,1’-偶氮双(环己烷-1-甲腈)(V40)、2,2’-偶氮二[N-(2-丙烯基)-2-甲基丙酰胺](VF096)、2,2’-偶氮二(N-丁基-2-甲基丙酰胺)(VAm110)。作为过氧化物系自由基引发剂的具体例,可以举出过氧化苯甲酰、二枯基过氧化物、叔丁基过氧化氢、过氧化苯甲酸叔丁酯(BPB)、二(4-叔丁基环己基)过氧化二碳酸酯(PERKADOX16)、过氧化氢、过氧化二硫酸钾。这些自由基引发剂可以单独使用一种,也可以合用两种以上。
另外,本发明当然也可以为基于式(3)而生成的接枝聚合物、或作为式(1)所示的引发剂来体现的物质。
特别是,作为在有机催化剂的作用下与乙烯基系单体进行活性自由基聚合的引发剂来体现的情况下,在主链中具有下述式(1)所示的重复单元。
[化学式6]
此处,R1:-COO-(CH2)a-OCO-
R2、R3、R4、R5、R6:氢原子、芳香族基团、脂肪族基团
a=2~5
另外,R1:连接基团(可以包含醚键或酯键的碳原子数为1~30的直链状、支链状或环状的亚烷基、芳香族基团)更优选为下述通式(A)(式中,Z1、Z2相互独立地为氧原子、或者下述通式(B)。此处,R10表示直链状、支链状或环状的亚烷基,R11表示氢原子、或者脂肪族基团。
[化学式7]
[化学式8]
另外,R1:连接基团也可以作为通式(C)来体现(式中,Ar表示具有或不具有取代基的芳香族基团)。
[化学式9]
(C)-Ar—
R2、R3、R4、R5、R6、R11中的脂肪族基团含有具有或不具有取代基的直链或支链状的碳原子数为1~12的烷基。在脂肪族基团经取代的情况下,取代基的数量只要能够进行取代就没有特别限制,为1个或多个。
另外,作为可以对脂肪族基团进行取代的基团,可以举出卤原子、具有或不具有取代基的直链或支链状的碳原子数为1~12的烷基、具有或不具有取代基的芳香族基团、具有或不具有取代基的非芳香族杂环式基团、直链或支链状的碳原子数为1~12的烷氧基、氰基或硝基等。
R2、R3、R4、R5、R6、R11中的芳香族基团可以举出芳香族烃环基或芳香族杂环基,具体而言,可以举出苯基、联苯基、三联苯基、萘基、联萘基、薁基、蒽基、菲基、呋喃基(フラレニル)、呋喃基、噻吩基、吡咯基、吡唑基、咪唑基、异噁唑基、噻唑基、噻二唑基、吡啶基、苯并呋喃基、吲哚基、苯并噻唑基、咔唑基等。
该芳香族基团可以经取代,该情况下的取代基的数量只要能够进行取代就没有特别限制,为1个或多个。
另外,作为可以对芳香族基团进行取代的基团,可以举出卤原子、具有或不具有取代基的直链或支链状的碳原子数为1~12的烷基、具有或不具有取代基的芳香族基团、具有或不具有取代基的非芳香族杂环式基团、羧基、直链或支链状的碳原子数为1~12的烷氧基、氰基或硝基等。
下面举出实施例来具体说明本发明,但本发明不受下述实施例的任何限定。下述实施例中的分子量分布的测定方法如下所述。
[分子量分布测定]
分子量多分散指数(下文中简称为PDI)是由PDI=Mw/Mn表示的数值。此处,Mw为重均分子量、Mn为数均分子量。以下所示的Mn和PDI是使用凝胶渗透色谱(GPC;Shodex公司制造的GPC-101)、使用10mmol/L溴化锂N,N-二甲基甲酰胺(DMF)溶液或四氢呋喃(THF)作为洗脱液而得到的标准聚甲基丙烯酸甲酯(PMMA)换算分子量。
合成出式(1)所示的重复单元为化学式4的化合物。以下,将主链中具有化学式4所示的重复单元的化合物称为PHEMA-EMA-I。PHEMA-EMA-I的重复单元的分子量为357。在实施例之前,在参考例中对作为原料的聚(甲基丙烯酸-2-羟基乙酯)(下文中简称为PHEMA)的制造方法进行说明。
[主链聚合物(PHEMA)的制造(参考例)]
在安装有搅拌机、温度计和氮气导入管的反应装置中添加二乙二醇二甲醚(下文中简称为DMDG)11质量份、甲基丙烯酸-2-羟基乙酯(下文中简称为HEMA)100质量份、碘0.2质量份、四正丁基碘化铵(下文中简称为Bu4NI)2.8质量份、作为引发剂的2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)[商品名:V-70(下文中简称为V-70)、和光纯药公司制造]1.5质量份。然后,一边导入氮气一边搅拌,加热至50℃。将反应体系保持为50℃的同时聚合3小时。使用作为不良溶剂的己烷,通过再沉淀回收对上述反应混合物进行纯化,得到PHEMA。对于所得到的PHEMA,使用10mmol/L溴化锂N,N-二甲基甲酰胺溶液作为洗脱液,利用GPC通过聚甲基丙烯酸甲酯换算测定出分子量。
将基于上述参考例制作的PHEMA作为原料,在实施例1、实施例2中对PHEMA-EMA-I的制造方法进行说明。
[化学式10]
实施例1
[聚合引发基团向主链聚合物(PHEMA)中的导入第1方法]
向装有磁力搅拌子的反应装置中添加PHEMA(Mn=23000、PDI=1.41)2g、吡啶30mL后,加入2-溴异丁酰溴17.7g,在20℃下搅拌30分钟。对于上述反应混合物,在过滤后使用作为不良溶剂的水,通过再沉淀回收进行纯化。接着,称量所得到的析出物5g,加入丙酮15mL、碘化钠(下文中简称为NaI)6.3g。然后,在80℃下在氮气气氛下搅拌13.5小时。对生成的溴化钠进行过滤后,将反应混合物使用作为不良溶剂的1重量%亚硫酸氢钠水溶液通过再沉淀回收进行纯化,以收量3.9g得到PHEMA-EMA-I。通过利用THF溶剂的GPC测定分子量,结果以聚甲基丙烯酸甲酯换算计,Mn为27000,PDI为1.51。
1H-NMR(400MHz、CDCl3)δ:4.33(t、2H)、4.21(t、2H)、2.12(s、6H)、2.03-1.39(m、2H)、1.22-0.81(m、3H)。
实施例2
[聚合引发基团向主链聚合物(PHEMA)中的导入第2方法]
向装有磁力搅拌子的反应装置中添加二氯甲烷200mL、PHEMA(Mn=17400、PDI=1.73)20.8g、吡啶15.8g后,加入2-溴异丁酰溴44.1g和二氯甲烷50mL的混合物,搅拌30分钟。对于上述反应混合物,在过滤后使用作为不良溶剂的甲醇,通过再沉淀回收进行纯化。接着,使所得到的析出物干燥后称量20g,加入乙腈140mL、NaI32.2g。然后,在80℃下在氮气气氛下搅拌17小时。对生成的溴化钠进行过滤后,将反应混合物使用作为不良溶剂的甲醇通过再沉淀回收进行纯化,以收量20.3g得到PHEMA-EMA-I。通过利用THF溶剂的GPC测定分子量,结果以聚甲基丙烯酸甲酯换算计,Mn为50000,PDI为1.4。
1H-NMR(400MHz、CDCl3)δ:4.33(t、2H)、4.18(t、2H)、2.10(s、6H)、2.03-1.58(m、2H)、1.52-0.62(m、3H)。
实施例3
在实施例3中对基于导入有聚合引发基团的PHEMA-EMA-I的接枝聚合物的制造法进行说明。
[接枝聚合物的制造]
在100mL茄形瓶中将作为单体的甲基丙烯酸己酯(HMA)7.1534g、作为烷基碘的PHEMA-EMA-I(Mn=27000、PDI=1.51)0.300g、作为催化剂的四丁基碘化铵(下文中简称为Bu4NI)0.1522g、作为溶剂的二乙二醇二甲醚(下文中简称为DMDG)4.9689g进行混合,利用氩气置换残存氧,将该反应溶液加热至80℃,由此进行聚合反应。反应时间为6小时。根据高效液相色谱(HPLC),单体的聚合率为44%。通过利用THF溶剂的GPC测定分子量,结果以聚甲基丙烯酸甲酯换算计,Mn为300000,PDI为3.3。
Claims (5)
1.一种接枝聚合物的制造方法,其特征在于,通过在有机催化剂的作用下使主链中具有下述式(1)所示的重复单元的化合物与乙烯基系单体进行活性自由基聚合而制造接枝聚合物,
[化学式11]
此处,R1为连接基团,是可以包含醚键、酰胺键或酯键的碳原子数为1~30的直链状、支链状或环状的亚烷基、芳香族基团;
R2、R3、R4、R5、R6为氢原子、芳香族基团、脂肪族基团;
n=1~5。
2.如权利要求1所述的接枝聚合物的制造方法,其特征在于,在由胺化合物、膦化合物、膦酸酯化合物、鏻盐、碘化酰亚胺化合物或铵化合物中的任一种构成的有机催化剂的作用下,进行上述活性自由基聚合。
3.一种接枝聚合物,其特征在于,其是通过权利要求1或2所述的接枝聚合物的制造方法制造的。
4.一种接枝聚合物的引发剂,其特征在于,其作为权利要求1或2所述的接枝聚合物的制造方法中的与乙烯基系单体进行活性自由基聚合的引发剂来使用,其在主链中具有下述式(1)所示的重复单元,
[化学式12]
5.一种接枝聚合物的引发剂,其特征在于,其作为在有机催化剂的作用下与乙烯基系单体进行活性自由基聚合的引发剂来使用,其在主链中具有下述式(1)所示的重复单元,
[化学式13]
此处,R1为-COO-(CH2)a-OCO-;
R2、R3、R4、R5、R6为氢原子、脂肪族基团;
a=2~5。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998040415A1 (en) * | 1997-03-11 | 1998-09-17 | Carnegie Mellon University | Improvements in atom or group transfer radical polymerization |
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US5789487A (en) | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
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WO2013150751A1 (ja) | 2012-04-02 | 2013-10-10 | 東洋ゴム工業株式会社 | ケイ素化合物及びその製造方法、並びにその利用 |
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JP2014117672A (ja) | 2012-12-18 | 2014-06-30 | Kao Corp | 分散剤 |
US9926386B2 (en) * | 2014-02-13 | 2018-03-27 | Kyoto University | Living radical polymerization catalyst, and polymer production method using same |
JP6381945B2 (ja) * | 2014-04-08 | 2018-08-29 | 東洋ゴム工業株式会社 | 共重合体及びその製造方法、並びにゴム組成物及び空気入りタイヤ |
JP6254239B2 (ja) * | 2016-02-29 | 2017-12-27 | 大日精化工業株式会社 | ポリマーの製造方法 |
WO2017150287A1 (ja) | 2016-02-29 | 2017-09-08 | 大日精化工業株式会社 | ポリマーの製造方法及びラジカル重合の開始基含有化合物 |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998040415A1 (en) * | 1997-03-11 | 1998-09-17 | Carnegie Mellon University | Improvements in atom or group transfer radical polymerization |
JP2015227407A (ja) * | 2014-05-30 | 2015-12-17 | 住友化学株式会社 | アクリル樹脂 |
Non-Patent Citations (1)
Title |
---|
MIRCEA TEODORESCU ETAL: ""Grafting syrene onto poly(vinyl acetate) by free radical chain transfer reactions"", 《REACTIVE & FUNCATIONAL POLYMERS》 * |
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