CN1307601A - 一种聚合方法 - Google Patents

一种聚合方法 Download PDF

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CN1307601A
CN1307601A CN99808054A CN99808054A CN1307601A CN 1307601 A CN1307601 A CN 1307601A CN 99808054 A CN99808054 A CN 99808054A CN 99808054 A CN99808054 A CN 99808054A CN 1307601 A CN1307601 A CN 1307601A
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V·C·吉布森
D·J·欧文
P·A·卡梅伦
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    • C—CHEMISTRY; METALLURGY
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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    • C08F220/00—Copolymers 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
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    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F20/00—Homopolymers and copolymers 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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Abstract

由相应的乙烯基单体制备乙烯基聚合物的一种聚合方法,该方法包括在催化剂体系的存在下反应乙烯基单体的步骤,该催化剂体系含有a)通式(Ⅰ)的金属配合物,其中A选自镍、铁、钴、铬、锰、钛、锆、钒和稀土金属;L1、L2、L3和L4是配位体,和b)通式(Ⅱ)的路易斯酸,其中W、Y或Z中的至少一种能与A形成配位键,且其它W、Y或Z是体积庞大的基团;D选自铝、镁、锌和硼。

Description

一种聚合方法
本发明涉及在催化剂体系的存在下制备乙烯基聚合物的一种聚合方法。
活性或不死的聚合是一种不能自然终止的聚合反应。每个引发剂分子产生一个增长链，以使聚合物随时间的延长线性增长。所以可将聚合度控制在一定程度上。Inoue已开发了这种方法，其中用通式为(TPP)AIX的卟啉铝作为引发剂，通过从来自氙弧的辐射将甲基丙烯酸酯类和丙烯酸酯类进行活性聚合(Polym.Prepr.Jpn(英文版)1992，41，E93(IIID-06)和E96(IIID-12)。
Figure A9980805400041
                                               (TPP)AIX，
                                   其中X＝CH3或CH2CH2CH3在环境温度下，发现每个(TPP)AIX分子产生一个聚合物链并获得对分子量的优异控制。
结果Inoue发现，另外加入路易斯酸可大大提高链增长速率。例如发现在辐照光的存在下由(TPP)AlMe引发的甲基丙烯酸甲酯(MMA)的聚合反应在2.5小时后生成6.1％的聚甲基丙烯酸甲酯。随着路易斯酸例如体积庞大的苯酚铝的加入，在3秒内发生定量聚合。最近，Inoue已公开了不需要存在辐照光的体系。例如在路易斯酸的存在下由(TPP)AIX(其中X＝丙硫基(SPropyl))引发MMA的聚合，其中于80℃在1.5分钟后有完全的单体转化率(T Kodeira和K Mori，Macromol.Chem.RapidCommun.1990，11，645)。但是用该体系制备的聚合物分子量低，例如22000。
据Inoue报导，引发反应是(TPP)AIX配合物与单体在辐照光的存在下反应形成烯醇化物引发剂。然后该烯醇化物可与另外的单体在作为活化剂的路易斯酸的存在下反应以生成聚合物链。
E.A.Jeffery等人在 金属有机化学杂志(1974，74，365、372页)已公开了通过促进三甲基铝对α，β-不饱和酮类的1，4-加成反应来用镍(乙酰丙酮)2催化烯醇化铝的形成。催化烯醇化物的形成的镍配合物与通过金属烯醇化物进行的聚合反应有关，其中该金属烯醇化物含有基于钐和锆的现有金属茂引发剂。
本发明的目的是提供一种催化剂体系，用于将乙烯基单体聚合成相应的聚合物，从而迅速地进行聚合反应并可控制聚合反应。
因此，本发明提供由相应的乙烯基单体制备乙烯基聚合物的聚合方法，该方法包括在催化剂体系的存在下反应乙烯基单体的步骤，该催化剂体系含有
a)通式(I)的金属配合物其中A选自镍、铁、钴、铬、锰、钛、锆、钒和稀土金属；L1、L2、L3和L4是配位体，和
b)通式(II)的路易斯酸
Figure A9980805400052
其中W、Y或Z中的至少一种能与A形成配位键，且其它W、Y或Z是体积庞大的基团；D选自铝、镁、锌和硼。
对于稀土金属，我们指镧和镧系元素。
可根据本发明制备的乙烯基聚合物包括相应的乙烯基单体的均聚物和共聚物，乙烯基单体例如(烷基)丙烯酸及其烷基酯类、官能化(烷基)丙烯酸及其烷基酯类(例如羟基、卤素、胺官能化的)、苯乙烯、乙酸乙烯酯、丁二烯。对于(烷基)丙烯酸类，我们指可使用烷基丙烯酸类或类似的丙烯酸类。对于均聚物和共聚物，单体优选是(烷基)丙烯酸及其烷基酯类，更优选是(甲基)丙烯酸烷基酯类。这些聚合反应可通过能制备结构共聚物例如嵌段、ABA和星形共聚物的方式来进行。
聚合反应可在溶剂的存在下进行，例如甲苯、二氯甲烷和四氢呋喃，或在本体单体中进行。该聚合反应优选在-100℃至150℃之间进行，更优选-50℃至50℃，特别是15℃至40℃。
化合物(II)中的金属A优选是铁、钴或镍，更优选镍。金属可以各种氧化态存在，例如0、1、2或3。配位体L1、L2、L3和L4可表示为全部单齿配位体、2个单齿和1个双齿配位体的组合，其中L1、L2、L3和L4的一对配位体代表双齿配位体，其它两个L1、L2、L3和L4的配位体代表2个不同的单齿配位体，或2个双齿配位体。优选L1、L2、L3和L4代表2个双齿配位体，更优选2个乙酰丙酮化物配位体或2个双齿环辛二烯配位体。
在化合物(II)中，连接于D上的基团选自W、Y或Z中的一种，其本身能与A形成配位键，该基团优选选自烷基、卤素、烷氧基、芳氧基和酯，更优选C1-C10碳原子的烷基，更特别是甲基。剩余的体积庞大的基团优选与上述相同，特别是酚盐或取代的酚盐或硫醇盐。D优选是铝。虽然不希望受理论限制，但我们认为引发反应包括在化合物(I)的存在下将选自化合物(II)的D中的W、Y或Z之一的基团转移到金属A上。所以，对本发明方法必要的是W、Y或Z的至少一种能与A形成键。
在该催化剂体系内，化合物(I)的摩尔数对化合物(II)的摩尔数之比优选在1∶0.1至1∶100的范围内，更优选1∶0.2至1∶10。特别优选这样的体系，其中化合物(I)的摩尔数对化合物(II)的摩尔数之比是1∶3。这些催化剂体系可根据本发明的方法用于单体浓度在以化合物(I)的摩尔数计的1-20,000摩尔范围内的聚合反应。
虽然认为聚合时间取决于单体和溶剂的类型，但是在其它因素中，对于均聚物，聚合典型地在小于5分钟内完成。通过本发明方法由溶液聚合制备的均聚物和共聚物可具有比通过现有的溶液阴离子或自由基聚合方法制备的相同均聚物和共聚物更高的间同立构含量。
通过以下实施例说明本发明。
实施例1聚甲基丙烯酸甲酯(PMMA)的制备
在烧瓶中于氮气下制备MMA(1克，200摩尔当量的化合物(I))在二氯甲烷(2毫升)(DCM)中的溶液。向第二个烧瓶中在氮气下加入乙酰丙酮化镍(12.8毫克，0.05摩尔)(化合物I)和甲基铝双(2，6-二叔丁基-4-甲基酚盐)(72.0毫克，0.15摩尔)(化合物II)。将在DCM中的MMA加入第二个烧瓶中，并将反应混合物搅拌5分钟。加入甲醇(0.5毫升)以终止反应，并用DCM(10毫升)稀释反应混合物。从10倍过量的酸化(1％盐酸)甲醇中沉淀PMMA。
PMMA的产率是95％。
在该实施例中，化合物(I)对化合物(II)的摩尔比是1∶3，且反应在环境温度下进行。
与计算值20000相比，PMMA的实际分子量为118300。该计算值基于镍(乙酰丙酮)2。多分散度为1.63，间同立构百分率是72％。
通过在Bruker AC-250机器上于250MHz下从PMMA的1H NMR检测三单元组(三个连续的单体单元)信号的相对积分来计算PMMA立构规整度。这些三单元组对应于间同立构、全同立构和杂同立构的含量。
Mn和多分散度值通过凝胶渗透色谱(GPC)来测定。所用的GPC检测器是配备有Viscotek Trisec软件的Knauer差示折光仪。将试样注入两个线形10微米的色谱柱中(用聚苯乙烯校正)，用氯仿作为洗脱剂，流动速率为1毫升/分钟。

Claims (8)

1.由相应的乙烯基单体制备乙烯基聚合物的一种聚合方法，该方法包括在催化剂体系的存在下反应乙烯基单体的步骤，该催化剂体系含有
a)通式(I)的金属配合物
Figure A9980805400021
其中A选自镍、铁、钴、铬、锰、钛、锆、钒和稀土金属；L1、L2、L3和L4是配位体，和
b)通式(II)的路易斯酸
Figure A9980805400022
其中W、Y或Z中的至少一种能与A形成配位键，且其它W、Y或Z是体积庞大的基团；D选自铝、镁、锌和硼。
2.权利要求1所述的聚合方法，其中所述乙烯基单体选自(烷基)丙烯酸及其烷基酯类、官能化(烷基)丙烯酸及其烷基酯类。
3.权利要求1或2中任一项所述的聚合，其中所述化合物(I)中的A是铁、钴或镍。
4.权利要求1-3中任一项所述的聚合，其中所述化合物(I)中的配位体L1、L2、L3和L4选自全部单齿、2个单齿和1个双齿配位体的组合或2个双齿配位体。
5.权利要求1-4中任一项所述的聚合，其中所述化合物(II)中的D是铝。
6.权利要求1-5中任一项所述的聚合，其中所述化合物(III)中的基团W、Y或Z中的一种是含C1-C10碳原子的烷基。
7.权利要求1-6中任一项所述的聚合，其中化合物(I)的摩尔数对化合物(II)的摩尔数之比在1∶0.1至1∶100的范围内。
8.权利要求1-7中任一项所述的聚合，其中化合物(I)的摩尔数对化合物(II)的摩尔数之比在1∶0.2至1∶10的范围内。
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