CN101070367B - Method for preparing block copolymer containing polyvinylpyridine in non-polarized solution - Google Patents

Method for preparing block copolymer containing polyvinylpyridine in non-polarized solution Download PDF

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CN101070367B
CN101070367B CN 200710099590 CN200710099590A CN101070367B CN 101070367 B CN101070367 B CN 101070367B CN 200710099590 CN200710099590 CN 200710099590 CN 200710099590 A CN200710099590 A CN 200710099590A CN 101070367 B CN101070367 B CN 101070367B
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polymerization
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block copolymer
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CN101070367A (en
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吴友平
张立群
李琼
韩丙勇
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北京化工大学
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Abstract

The invention relates to a method of preparing block copolymers comprising p-vinyl pyridines in nonpolar solvents, which relates to the field of macromolecular compound composition. The method uses negative ion polymerization to prepare block copolymers comprising polar monomer vinyl pyridine polymer chain, in non-polar solvents, such as cyclohexane, etc. The polymeric process has two steps of feeding raw materials, i.e. firstly, organolithium is used to initiate the polymerization of non-polar monomers, such as styrene, butadiene, isoprene, etc., and then alkyl aluminum, alkyl magnesium, etc. is used to reduce the activity of the polymer, and finally, vinyl pyridine monomer is fed to polymerize. The polymeric method is negative ion dispersion polymerization, and its products are microspheres formed by diblock copolymers. The polymer has broad uses, such as material surface modification, high-molecular material compatilizer. Moreover, the microsphere could be a new kind of reinforcing filler.

Description

一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物方法 Block copolymer-containing polyvinyl pyridine to prepare a non-polar solvent

技术领域 FIELD

[0001] 本发明涉及高分子化合物合成领域,特别涉及负离子聚合方法。 [0001] The present invention relates to the synthesis of a polymer compound, and more particularly relates to anionic polymerization method. 背景技术 Background technique

[0002] 负离子聚合是制备嵌段共聚物很好的方法。 [0002] The anion polymerization is a good method of preparing block copolymers. 非极性单体如苯乙烯、丁二烯、异戊二烯等的负离子聚合控制技术已经很成熟了,并且有多种嵌段共聚物产品面世。 Anion non-polar monomers such as styrene, butadiene, isoprene polymerization control technology has matured, a variety of block copolymers and products available. 目前,极性-非极性双亲性嵌段共聚物具有更广泛的应用领域。 Currently, polar - nonpolar amphiphilic block copolymer having a wider range of applications. 但采用负离子聚合方法制备含极性嵌段共聚物难度比较大,这是因为,极性单体的负离子聚合要求条件更苛刻。 But the use of anionic polymerization process for preparing block copolymers containing polar more difficult, because, polar monomer anion polymerization conditions more stringent requirements. 如乙烯基吡啶的负离子聚合表现为聚合速度相当快,难以控制,且存在副反应。 The anionic polymerization of vinylpyridine very fast performance of the polymerization is difficult to control, and the presence of side reactions. 此外,乙烯基吡啶的聚合物不溶于环己烷等非极性溶剂。 Further, the vinylpyridine polymer is insoluble in a nonpolar solvent such as cyclohexane. 所以采用负离子聚合制备含聚乙烯基吡啶的嵌段共聚物, 其反应主要在极性溶剂中进行。 Therefore, the block copolymer prepared using anionic polymerization containing polyvinyl pyridine, which reaction is mainly conducted in a polar solvent. Robert J6r0me等在9 : 1的必定/四氢呋喃中制备含聚4-乙烯基吡啶的嵌段共聚物(macromolecules,1997,30 (1),5596)。 Block copolymers must be prepared / tetrahydrofuran 1 containing poly-4-vinylpyridine (macromolecules, 1997,30 (1), 5596): Robert J6r0me like 9. 有时为了减少副反应, 还需在较低温度反应(如_78°C ),且必须采用'戴帽,技术(polymer,1998,39 (12),2615)。 Sometimes, in order to reduce side reactions, need the reaction at a lower temperature (e.g., _78 ° C), and must be 'capped, technique (polymer, 1998,39 (12), 2615). 一些研究人员尝试在非极性溶剂中实现2-乙烯基吡啶负离子聚合,但所选溶剂主要有苯、 甲苯等(macromolecules,2001,34,1192)。 Some researchers tried to achieve 2-vinylpyridine anionic polymerization in a nonpolar solvent, but solvents are selected as benzene, toluene and the like (macromolecules, 2001,34,1192). 这些溶剂毒性大,在工业上应用有困难。 These toxic solvents, difficulties in industrial application. 我们采用通过有机金属化合物降低引发活性的方式,在环己烷、己烷中实现了含聚乙烯基吡啶的嵌段共聚物的制备,该合成方法是一种负离子分散聚合,聚合过程直接形成聚合物微球。 We used organometallic compound reduces activity triggered manner, to achieve the preparation of a block copolymer containing polyvinyl pyridine in cyclohexane, hexane, which is a synthetic anion dispersion polymerization method, direct polymerization process to form a polymerization material microspheres.

[0003] 双亲性嵌段共聚物是一类用途广泛的材料,如不同聚合物间的相容剂、材料表面的改性等。 [0003] Amphiphilic block copolymers are a class of materials widely use, compatibilizing agent, surface modification and other materials, such as between the different polymers. 双亲性聚合物对溶剂具有选择性,因此能够进行自组装,形成新型材料。 Amphiphilic polymer selective solvent, it is possible to self-assemble to form a new material. 此外, 我们制备过程直接形成微球结构,外层为橡胶材料,内部聚乙烯基吡啶玻璃化温度比较高, 是一种潜在的橡胶材料补强剂。 Furthermore, we directly formed during the preparation of microspheres structure, the outer layer is a rubber material, polyvinyl pyridine inner glass transition temperature is relatively high, a potential rubber reinforcing agent.

发明内容 SUMMARY

[0004] 本发明的目的是实现在非极性溶剂中制备非极性单体与乙烯基吡啶的嵌段共聚物,并形成核壳型的纳米微球。 [0004] The object of the present invention is to realize a non-polar monomers prepared with block copolymers of vinyl pyridine in a non-polar solvent, and forming a core-shell nanoparticles.

[0005] 本发明是在干燥、无氧、装有有机溶剂的反应容器中加入引发剂和单体在一定温度下进行聚合实现的。 [0005] The present invention is in a dry, oxygen-free reaction vessel containing organic solvent is added the polymerization initiator and monomer at a temperature realized.

[0006] 本发明提供了一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物方法,其特征在于,包括以下步骤: [0006] The present invention provides a method for the block copolymer prepared in non-polar solvent containing polyvinyl pyridine, which is characterized by comprising the steps of:

[0007] 1)在有机溶剂中加入有机锂引发非极性单体聚合,聚合温度50°C -90°C,聚合时间0. 5-4小时;其中:有机锂是烷基锂、或苯基锂、或苄基锂、或烯丙基锂;非极性单体有苯乙烯、丁二烯、异戊二烯; [0007] 1) in an organic solvent is added an organolithium initiator nonpolar monomers, a polymerization temperature of 50 ° C -90 ° C, the polymerization time is 0. 5-4 hours; wherein: organolithium alkyllithium, or phenyl group lithium, lithium or benzyl, or allyl lithium; non-polar monomers are styrene, butadiene, isoprene;

[0008] 2)加入添加剂烷基铝或烷基镁,搅拌1-10分钟; [0008] 2) adding an additive magnesium aluminum alkyl or alkyl, stirred for 1-10 minutes;

[0009] 3)加入极性单体乙烯基吡啶在20°C -50°C聚合10-40分钟,得到极性-非极性两嵌段共聚物。 [0009] 3) addition of a polar monomer polymerized vinylpyridine 10 to 40 minutes at 20 ° C -50 ° C, to give a polar - nonpolar diblock copolymers.

[0010] 极性单体乙烯基吡啶有4-乙烯基吡啶和2-乙烯基吡啶,极性单体浓度为3〜 [0010] polar monomers include 4-vinyl pyridine and vinyl pyridine 2-vinyl pyridine, polar monomer concentration is 3 ~

321% wt ;有机溶剂是环己烷、己烷或二者的混合物。 321% wt; the organic solvent is a mixture of cyclohexane, hexane, or both.

[0011] 本发明引发剂为烷基锂、苯基锂、苄基锂、烯丙基锂等,用量为0. 5-15mmol每100 克单体总量。 [0011] The initiators of the present invention is an alkyl lithium, phenyl lithium, benzyl lithium, allyl lithium, in an amount of 0. 5-15mmol per 100 grams of total monomer. 使用不同的有机锂(RLi)、非极性单体与乙烯基吡唆,可以聚合出不同分子量和分子量分布的嵌段共聚物。 Using different organolithium (RLi), non-polar monomer and a vinyl pyridine instigate, the block copolymer may be polymerized different molecular weights and molecular weight distributions.

[0012] 本发明非极性单体为苯乙烯、丁二烯、异戊二烯,极性单体为4-乙烯基吡啶、2-乙烯基吡啶。 Non-polar monomers invention [0012] This styrene, butadiene, isoprene, polar monomer is 4-vinylpyridine, 2-vinylpyridine. 其中,极性单体占单体总量的70% -5% Wt0 Wherein the polar monomer comprises 70% -5% Wt0 total monomers

[0013] 本发明采用的添加剂为烷基铝或烷基镁,最好为三乙基铝、二正丁基镁、三异丁基铝等,其与引发剂的摩尔比为0. 2-2. 0,最好为0. 5-1. 2。 [0013] Additives employed in the present invention is an alkyl aluminum or alkyl magnesium, preferably triethyl aluminum, di-n-butylmagnesium, triisobutyl aluminum and the like, with a molar ratio of initiator is 0. 2- 2.0, preferably 0. 5-1. 2.

[0014] 该体系为溶液聚合体系,溶剂包括环己烷、正己烷及由这两种溶剂组成混和溶剂。 [0014] The system for the solution polymerization system, the solvent include cyclohexane, n-hexane, and a mixed solvent of these two solvents. 极性单体的浓度为5-30% Wt0 Concentration of the polar monomer is 5-30% Wt0

[0015] 本发明的效果:本发明采用添加烷基铝或烷基镁的方式降低了引发活性,实现了在非极性溶剂中对乙烯基吡啶负离子聚合的控制,合成出极性非极性两嵌段共聚物,其聚集体为核壳型纳米微球,微球直径在20-1000nm。 [0015] Effect of the Invention: The present invention uses an aluminum alkyl or alkyl Add the magnesium reduced priming activity, achieved in a non-polar solvent for controlling the anionic polymerization of vinyl pyridine, synthesized nonpolar polar diblock copolymers, which aggregates of core-shell nanospheres, microspheres diameter 20-1000nm.

具体实施方式 Detailed ways

[0016] 本发明的工艺过程以异戊二烯和4-乙烯基吡啶为例简述如下:首先采用正丁基锂引发异戊二烯在环己烷中聚合,聚合温度50°C -90°C ;聚合完成后加入烷基铝,然后加入4-乙烯基吡啶在20°C-50°C聚合。 [0016] The process of the present invention in an example 4-vinylpyridine and isoprene summarized as follows: First, using n-butyllithium initiator in cyclohexane isoprene polymerization, the polymerization temperature of 50 ° C -90 ° C; after completion of the polymerization an aluminum alkyl added, followed by the addition polymerization of 4-vinylpyridine in 20 ° C-50 ° C. 最后用用乙醇终止。 Finally terminated with ethanol. 经沉淀后真空干燥得聚异戊二烯-聚4-乙烯基吡啶嵌段共聚物,其聚集态呈外层为聚异戊二烯壳,内部为聚4-乙烯基吡啶核的纳米微球。 After drying in vacuo the precipitate poly isoprene - poly 4-vinyl pyridine block copolymer, which showed aggregation polyisoprene outer shell, the inner core is a poly 4-vinylpyridine nanospheres .

[0017] 使用凝胶渗透色谱仪对聚合物样品的Mn和MWD进行分析,核磁共振(NMR)对聚合物样品的单体比例和微观结构进行表征。 [0017] Using a gel permeation chromatograph of Mn and MWD polymer sample for analysis, nuclear magnetic resonance (NMR) of the monomer ratio and microstructure of the polymer sample were characterized. 将样品溶于有机溶剂,可采用激光粒度分析仪测试其粒径及其分布。 The sample is dissolved in an organic solvent, can be used to test laser particle size analyzer and a particle size distribution.

[0018] 下面的实例供进一步说明本发明的方法之用,但不应受此限制。 [0018] The following examples further illustrate the method for the present invention, but should not be limited thereto.

[0019] 实例1 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0019] Example 1: baked in an oven above 120 ° C for 4h conditions used for glass reaction vessel, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入50ml 环己烷,5克异戊二烯0. 2mmol正丁基锂在60°C下聚合两小时,然后加入0. 2mmol三乙基铝搅拌5分钟,最后加入2克4-乙烯基吡啶在30°C下聚合40小时。 IOOml take a polymerization bottle, 50ml of cyclohexane was added, 5 g of n-butyllithium 0. 2mmol isoprene polymerized for two hours at 60 ° C, followed by addition of 0. 2mmol triethylaluminum stirred for 5 minutes and finally 2 g 4-vinylpyridine polymerization at 30 ° C 40 h. 聚合溶液呈血红透明。 The polymerization solution was transparent blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn 为3. 5万,分子量分布1.2,单体转化率99. 8%。 The resulting polymer was measured molecular weight Mn of 35,000, a molecular weight distribution of 1.2, a monomer conversion of 99.8%.

[0020] 实例2 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0020] Example 2: The glass reaction vessel at 120 ° C oven bake conditions than 4h, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个250ml的聚合瓶,加入140ml环己烷,5克丁二烯0. 035mmol正丁基锂在60°C下聚合两小时,然后加入0. 07mmol三乙基铝搅拌1分钟,最后加入2克4-乙烯基吡啶聚合40分钟。 Take a 250ml bottle of the polymerization, was added 140ml of cyclohexane, 5 g of n-butyllithium 0. 035mmol butadiene polymerization at 60 ° C for two hours and then added 0. 07mmol triethylaluminum stirred for one minute and finally 2 g of 4-vinylpyridine polymerized for 40 minutes. 聚合溶液呈血红色。 The polymerization solution was blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn为20万,分子量分布1.3,单体转化率99.2%。 The molecular weight Mn of the resulting polymer obtained was 200,000, the molecular weight distribution of 1.3, 99.2% monomer conversion.

[0021] 实例3 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0021] Example 3: The glass reaction vessel at 120 ° C oven bake conditions than 4h, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入25ml 环己烷,5克苯乙烯1. 5mmol正丁基锂在60°C温度下聚合半小时,然后加入1. 2mmol三乙基铝搅拌10分钟,最后加入5克4-乙烯基吡啶聚合40分钟。 IOOml take a polymerization bottle, 25ml of cyclohexane, 5 g of styrene 1. 5mmol polymerization of n-butyllithium in a half hour 60 ° C for temperature, followed by the addition of triethylaluminum 1. 2mmol stirred for 10 minutes and finally 5 g of 4-vinylpyridine polymerized for 40 minutes. 聚合溶液呈血红色。 The polymerization solution was blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn为0. 7 万,分子量分布1. 38,单体转化率100%。 The resulting polymer was measured molecular weight Mn of 07,000, a molecular weight distribution of 1.38, 100% monomer conversion.

[0022] 实例4 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0022] Example 4: The reaction glass container in an oven bake 120 ° C for 4h above conditions, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入50ml 环己烷,2. 1克异戊二烯0. 2mmol正丁基锂在60°C温度下聚合两小时,然后加入0. 4mmol 二正丁基镁搅拌10分钟,最后加入4. 9克4-乙烯基吡啶聚合40分钟。 IOOml take a polymerization bottle, 50ml of cyclohexane was added, 2.1 g of n-butyllithium 0. 2mmol of isoprene polymerized for two hours and 60 ° C for temperature, followed by addition of di-n-butylmagnesium 0. 4mmol stirring 10 minutes and finally 4.9 g of 4-vinylpyridine polymerized for 40 minutes. 聚合溶液呈血红透明。 The polymerization solution was transparent blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn 为3. 2万,分子量分布1.2,单体转化率98.6%。 The resulting polymer was measured molecular weight Mn of 32,000, a molecular weight distribution of 1.2, 98.6% monomer conversion.

[0023] 实例5 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0023] Example 5: The baked in an oven above 120 ° C for 4h conditions with a glass reaction vessel, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入60ml 环己烷,5. 7克异戊二烯0. 2mmol正丁基锂在60°C温度下聚合两小时,然后加入0. 2mmol三异丁基铝搅拌5分钟,最后加入0. 3克4-乙烯基吡啶聚合10分钟。 IOOml take a polymerization bottle, 60ml of cyclohexane, 5.7 g of n-butyllithium 0. 2mmol isoprene polymerized at a temperature of 60 ° C for two hours and then added 0. 2mmol triisobutylaluminum stirred 5 minutes and finally 0.3 g of 4-vinylpyridine polymerization for 10 minutes. 聚合溶液呈血红透明。 The polymerization solution was transparent blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn 为3. 0万,分子量分布1.2,单体转化率99. 9%。 The resulting polymer was measured molecular weight Mn of 30,000, a molecular weight distribution of 1.2, a monomer conversion of 99.9%.

[0024] 实例6 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0024] Example 6: The baked in an oven above 120 ° C for 4h conditions with a glass reaction vessel, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个250ml的聚合瓶,加入IOOml环己烷,5克苯乙烯0. 3mmol正丁基锂在60°C温度下聚合两小时,然后加入0. 2mmol 三乙基铝搅拌5分钟,最后加入10克4-乙烯基吡啶聚合40分钟。 Take a 250ml bottle of the polymerization, cyclohexane was added IOOml 5 grams of styrene n-butyl lithium polymerization 0. 3mmol two hours at 60 ° C for temperature, then added 0. 2mmol triethylaluminum stirred for 5 minutes and finally 10 g of 4-vinylpyridine polymerized for 40 minutes. 聚合溶液呈血红色。 The polymerization solution was blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn 为5.0万,分子量分布1.30单体转化率99.8%。 The resulting polymer was measured molecular weight Mn of 50,000, molecular weight distribution 1.30 99.8% monomer conversion.

[0025] 实例7 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0025] Example 7: baked in an oven above 120 ° C for 4h conditions used for glass reaction vessel, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入50ml 环己烷,5克异戊二烯0. 2mmol正丁基锂在60°C温度下聚合两小时,然后加入0. 2mmol三乙基铝搅拌5分钟,最后加入2克4-乙烯基吡啶聚合30分钟。 IOOml take a polymerization bottle, 50ml of cyclohexane was added, 5 g of n-butyllithium 0. 2mmol isoprene polymerized at a temperature of 60 ° C for two hours and then added 0. 2mmol triethylaluminum stirred for 5 minutes, and finally 2 g of 4-vinylpyridine and polymerized for 30 minutes. 聚合溶液呈血红透明。 The polymerization solution was transparent blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn为3. 5万,分子量分布1. 15,单体转化率99.6%。 The resulting polymer was measured molecular weight Mn of 35,000, a molecular weight distribution of 1.15, 99.6% monomer conversion.

[0026] 实例8 :所用玻璃反应容器于烘箱中120°C条件下烘4h以上,反应前容器抽真空-烘烤-充氮,反复三次,聚合反应在氮气气氛中进行。 [0026] Example 8: The reaction vessel was a glass baked in an oven 120 ° C for 4h above conditions, the reaction vessel was evacuated before - Baking - nitrogen, repeated three times, the polymerization reaction is carried out in a nitrogen atmosphere. 取一个IOOml的聚合瓶,加入50ml 己烷,5克异戊二烯0. 2mmol正丁基锂在60°C温度下聚合两小时,然后加入0. 2mmol 二正丁基镁搅拌5分钟,最后加入2克4-乙烯基吡啶聚合30分钟。 IOOml take a polymerization bottle, 50ml of hexane was added, 5 g of n-butyllithium 0. 2mmol isoprene polymerized at a temperature of 60 ° C for two hours and then added di-n-butylmagnesium 0. 2mmol stirred for 5 minutes, and finally 2 g of 4-vinylpyridine and polymerized for 30 minutes. 聚合溶液呈血红透明。 The polymerization solution was transparent blood red. 用少量甲醇终止,大量乙醇沉淀,真空干燥得聚合物以备测试。 Terminates with a small amount of methanol, a large number of ethanol precipitation, and dried under vacuum to prepare a polymer test. 测得所得聚合物的分子量Mn为3. 5万,分子量分布1.2,单体转化率99.7%。 The resulting polymer was measured molecular weight Mn of 35,000, a molecular weight distribution of 1.2, 99.7% monomer conversion.

Claims (4)

1. 一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物的方法,其特征在于,包括以下步骤:1)在非极性有机溶剂中加入有机锂引发非极性单体聚合,聚合温度50°c "90聚合时间0. 5-4小时;其中:有机锂是烷基锂、或苯基锂、或苄基锂、或烯丙基锂,用量为0. 5-15mmol每100克单体总量;非极性单体有苯乙烯、丁二烯或异戊二烯;2)加入添加剂烷基铝或烷基镁,搅拌1-10分钟;3)加入极性单体乙烯基吡啶在20°C -50°C聚合10-40分钟,极性单体浓度为3%〜 21% wt ;得到极性-非极性两嵌段共聚物;其中极性单体占单体总量的70% -5% wt,极性单体的浓度为5-30% wt。 1. A method for the block copolymer containing a non-polar solvent to prepare polyvinyl pyridine, which is characterized in that it comprises the following steps: 1) adding an organic lithium initiator in a nonpolar organic solvent a non-polar monomers The polymerization temperature is 50 ° c "90 hour polymerization time 0. 5-4; wherein: organolithium alkyllithium, lithium or phenyl, or benzyl lithium, allyl lithium, or, each in an amount of 0. 5-15mmol 100 g of the total monomers; non-polar monomers are styrene, butadiene or isoprene; 2) additives alkylaluminum or alkyl magnesium, stirred for 1-10 minutes; 3) addition of a polar monomer vinylpyridine polymerization is 20 ° C -50 ° C 10-40 minutes, the polar monomer concentration of 3% ~ 21% wt; obtained polar - nonpolar diblock copolymers; wherein the polar monomer comprises a single 70% -5% of the total body wt, concentration of the polar monomer is 5-30% wt.
2.根据权利要求1所述的一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物的方法,其特征在于:极性单体乙烯基吡啶有4-乙烯基吡啶和2-乙烯基吡啶。 The method of one non-polar block copolymer of claim 1 prepared in solvent-containing polyvinyl pyridine claim, wherein: there are polar monomers vinylpyridine 4-vinylpyridine and 2- vinyl pyridine.
3.根据权利要求1所述的一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物的方法,其特征在于:非极性有机溶剂是环己烷、己烷或二者的混合物。 3. The method of claim 1 non-polar solvent in the preparation of a block copolymer containing polyvinyl pyridine claim, wherein: the non-polar organic solvent is cyclohexane, hexane, or both mixture.
4.根据权利要求1所述的一种非极性溶剂中制备含聚乙烯基吡啶的嵌段共聚物的方法,其特征在于:添加剂为三乙基铝、二正丁基镁、三异丁基铝,其与引发剂的摩尔比为0. 2-2. O0 4. The method of one non-polar block copolymer of claim 1 prepared in solvent-containing polyvinyl pyridine claim, wherein: the additive is triethyl aluminum, di-n-butylmagnesium, triisobutyl aluminum group, with the molar ratio of initiator is 0. 2-2. O0
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