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    Process for polymerizing conjugated dienes
    1.
    发明授权
    Process for polymerizing conjugated dienes 失效
    聚合共轭二烯的方法

    公开(公告)号：US4174431A

    公开(公告)日：1979-11-13

    申请号：US937007

    申请日：1978-08-25

    申请人： Adel F. Halasa ,  James E. Hall ,  Donald N. Schulz

    发明人： Adel F. Halasa ,  James E. Hall ,  Donald N. Schulz

    IPC分类号： B01J31/12 ,  C08F36/04 ,  C08F4/50 ,  C08F4/08 ,  C08F4/54

    CPC分类号： B01J31/128 ,  B01J31/122 ,  C08F36/04

    摘要： The process and catalyst system disclosed herein comprises the polymerization of a conjugated diene such as 1,3-butadiene in hydrocarbon solution in the presence of a new catalyst composition comprising:(a) a dihydrocarbyl magnesium compound of 1-10 carbon atoms, preferably a dialkyl magnesium having 3-8 carbon atoms in each alkyl group, and(b) an alkali metal compound of the formula R(SM).sub.n, R'.sub.2 NM, R'NHM or RC.tbd.CM, wherein R is a hydrocarbyl radical of 1-10 carbon atoms, preferably alkyl, n is 1, 2 or 3, M is Li, Na or K, and R' is a hydrocarbyl radical of 1-10 carbon atoms or an acyl radical of 1-10 carbon atoms.This process is particularly advantageous in that the polymer product can be controlled to have only a relatively small amount of 1,2 structure in accordance with the polymerization temperature. For example, at 125.degree. C. with Li compounds, the product generally has a 1,2 content of 12.6% or less; at 50.degree. C., 10.6% or less; and at 25.degree. C., 7% or less. Where 1,2 contents of 17-25% are desired, these may be obtained by using the Na compounds, and when 1,2 contents of 37-54% are desired, these may be obtained by using K compounds. Where even higher 1,2 contents are desired, they may be obtained by using an amine, such as tetramethylethylenediamine, as an additional catalyst component.

    摘要翻译： 本文公开的方法和催化剂体系包括在新的催化剂组合物存在下在烃溶液中共轭共轭二烯如1,3-丁二烯的聚合，其包含：（a）1-10个碳原子的二烃基镁化合物，优选 每个烷基中具有3-8个碳原子的二烷基镁，和（b）式R（SM）n，R'2NM，R'NHM或RC 3BOND CM的碱金属化合物，其中R是1的烃基 -10个碳原子，优选烷基，n为1,2或3，M为Li，Na或K，R'为1-10个碳原子的烃基或1-10个碳原子的酰基。 该方法特别有利的是，根据聚合温度，聚合物产物可被控制为仅具有相对少量的1,2结构。 例如，在125℃下用Li化合物，该产物通常具有12.6％或更少的1,2含量; 在50℃，10.6％以下; 在25℃，7％以下。 当需要17-25％的1,2含量时，这些可以通过使用Na化合物获得，当需要37-54％的1,2含量时，可以通过使用K化合物来获得。 当需要甚至更高的1,2目录时，它们可以通过使用诸如四甲基乙二胺的胺作为另外的催化剂组分来获得。

    Dehydrocarbyl magnesium and an alkali metal compound catalyst composition for polymerizing conjugated dienes
    2.
    发明授权
    Dehydrocarbyl magnesium and an alkali metal compound catalyst composition for polymerizing conjugated dienes 失效
    脱氢烃基镁和用于聚合共轭二烯的碱金属化合物催化剂组合物

    公开(公告)号：US4139490A

    公开(公告)日：1979-02-13

    申请号：US848958

    申请日：1977-11-07

    申请人： Adel F. Halasa ,  James E. Hall ,  Donald N. Schulz

    发明人： Adel F. Halasa ,  James E. Hall ,  Donald N. Schulz

    IPC分类号： B01J31/02 ,  B01J31/12 ,  C08F36/04 ,  C08F4/46 ,  C08F4/48 ,  C08F4/50

    CPC分类号： B01J31/128 ,  B01J31/0228 ,  B01J31/122 ,  C08F36/04

    摘要： The process and catalyst system disclosed herein comprises the polymerization of a conjugated diene such as 1,3-butadiene in hydrocarbon solution in the presence of a new catalyst composition comprising:(a) a dihydrocarbyl magnesium compound of 1-10 carbon atoms, preferably a dialkyl magnesium having 3-8 carbon atoms in each alkyl group, and(b) an alkali metal compound of the formula R(SM).sub.n, R'.sub.2 NM, R'NHM or RC.tbd.CM, wherein R is a hydrocarbyl radical of 1-10 carbon atoms, preferably alkyl, n is 1, 2 or 3, M is Li, Na or K, and R' is a hydrocarbyl radical of 1-10 carbon atoms or an acyl radical of 1-10 carbon atoms.This process is particularly advantageous in that the polymer product can be controlled to have only a relatively small amount of 1,2 structure in accordance with the polymerization temperature. For example, at 125.degree. C. with Li compounds, the product generally has a 1,2 content of 12.6% or less; at 50.degree. C., 10.6% or less; and at 25.degree. C., 7% or less. Where 1,2 contents of 17-25% are desired, these may be obtained by using the Na compounds, and when 1,2 contents of 37-54% are desired, these may be obtained by using K compounds. Where even higher 1,2 contents are desired, they may be obtained by using an amine, such as tetramethylethylenediamine, as an additional catalyst component.

    摘要翻译： 本文公开的方法和催化剂体系包括在新的催化剂组合物的存在下在烃溶液中共轭二烯如1,3-丁二烯的聚合，其包含：

    Process for production of polymers having increased 1,2-microstructure
    3.
    发明授权
    Process for production of polymers having increased 1,2-microstructure 失效
    具有增加的1,2-微结构的聚合物的生产方法

    公开(公告)号：US4537939A

    公开(公告)日：1985-08-27

    申请号：US617407

    申请日：1984-06-04

    申请人： James E. Hall ,  Donald N. Schulz

    发明人： James E. Hall ,  Donald N. Schulz

    IPC分类号： C08F36/04 ,  C08F4/48

    CPC分类号： C08F36/04

    摘要： A process and catalyst system is disclosed herein for the preparation of (co)polymers having a 1,2-microstructure of between about 20 and about 65 percent. These (co)polymers are prepared in a hydrocarbon or non-polar solvent from a monomer system which contains at least one 1,3-diene monomer. The catalyst system which is employed in the production of the (co)polymer is a combination of an anionic initiator based on lithium and a phosphine oxide modifier which is substituted with three saturated heterocyclic rings, each hetero ring containing one nitrogen atom and either four, five or six carbon atoms.

    摘要翻译： 本文公开了用于制备具有约20至约65％的1,2-微结构的（共）聚合物的方法和催化剂体系。 这些（共）聚合物由含有至少一种1,3-二烯单体的单体体系在烃或非极性溶剂中制备。 用于制备（共）聚合物的催化剂体系是由三价饱和杂环取代的基于锂的阴离子引发剂和氧化膦改性剂的组合，每个杂环含有一个氮原子， 五或六个碳原子。

    Catalyst system containing an anionic initiator based on lithium and phosphine oxide modifier
    4.
    发明授权
    Catalyst system containing an anionic initiator based on lithium and phosphine oxide modifier 失效
    含有基于锂和氧化膦改性剂的阴离子引发剂的催化剂体系

    公开(公告)号：US4476240A

    公开(公告)日：1984-10-09

    申请号：US394066

    申请日：1982-07-01

    申请人： James E. Hall ,  Donald N. Schulz

    发明人： James E. Hall ,  Donald N. Schulz

    IPC分类号： C08F4/00 ,  C08F4/42 ,  C08F4/48 ,  C08F36/04

    CPC分类号： C08F36/04

    摘要： A process and catalyst system is disclosed herein for the preparation of (co)polymers having a 1,2-microstructure of between about 20 and about 65 percent. These (co)polymers are prepared in a hydrocarbon or non-polar solvent from a monomer system which contains at least one 1,3-diene monomer. The catalyst system which is employed in the production of the (co)polymer is a combination of an anionic initiator based on lithium and a phosphine oxide modifier which is substituted with three saturated heterocyclic rings, each hetero ring containing one nitrogen atom and either four, five or six carbon atoms.

    摘要翻译： 本文公开了用于制备具有约20至约65％的1,2-微结构的（共）聚合物的方法和催化剂体系。 这些（共）聚合物由含有至少一种1,3-二烯单体的单体体系在烃或非极性溶剂中制备。 用于制备（共）聚合物的催化剂体系是由三价饱和杂环取代的基于锂的阴离子引发剂和氧化膦改性剂的组合，每个杂环含有一个氮原子， 五或六个碳原子。

    Polymerization using late transition metal catalyst complexes formed in situ
    5.
    发明授权
    Polymerization using late transition metal catalyst complexes formed in situ 失效
    使用晚期形成的过渡金属催化剂复合物进行聚合

    公开(公告)号：US06506859B1

    公开(公告)日：2003-01-14

    申请号：US09642487

    申请日：2000-08-18

    申请人： Abhimanyu O. Patil ,  Robert T. Stibrany ,  Stephen Zushma ,  Enock Berluche ,  Donald N. Schulz

    发明人： Abhimanyu O. Patil ,  Robert T. Stibrany ,  Stephen Zushma ,  Enock Berluche ,  Donald N. Schulz

    IPC分类号： C08F442

    CPC分类号： C08F10/00 ,  C08F110/02 ,  C08F210/02 ,  C08F4/54 ,  C08F2500/03 ,  C08F220/12

    摘要： The invention is directed towards the formation of polymers and copolymers using late transition metal polymerization catalyst complexes which are formed in situ. In the first process step of the instant invention, a composition having the formula MXZn is simultaneously contacted with a ligand and an activating cocatalyst. Referring to the formula, M is selected from the group consisting of Cu, Ag, and Au; X is selected from the group consisting of halides, hydride, triflate, acetates, borates, C1 through C12 alkyl, C1 through C12 alkoxy, C3 through C12 cycloalkyl, C3 through C12 cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, and any other moiety into which a monomer can insert; Z is selected from the group consisting of halides, hydride, triflate, acetates, borates, C1 through C12 alkyl, C1 through C12 alkoxy, C3 through C12 cycloalkyl, C3 through C12 cycloalkoxy, aryl, thiolates, carbon monoxide, cyanate, olefins, a neutral coordinating ligand, and any other moiety into which a monomer can insert; n equals 0, 1 or 2. In the second process step of the instant invention, olefinic monomers are contacted with the activated catalyst composition under polymerization conditions.

    摘要翻译： 本发明涉及使用在原位形成的后过渡金属聚合催化剂络合物形成聚合物和共聚物。 在本发明的第一工艺步骤中，具有式MXZn的组合物与配体和活化助催化剂同时接触。 参考式，M选自Cu，Ag和Au; X选自卤化物，氢化物，三氟甲磺酸盐，乙酸盐，硼酸盐，C1至C12烷基，C1至C12烷氧基，C3至C12环烷基，C3至C12环烷氧基，芳基，硫醇盐，一氧化碳，氰酸盐，烯烃和 单体可以插入的任何其他部分; Z选自卤化物，氢化物，三氟甲磺酸盐，乙酸盐，硼酸盐，C1至C12烷基，C1至C12烷氧基，C3至C12环烷基，C3至C12环烷氧基，芳基，硫醇盐，一氧化碳，氰酸盐，烯烃， 中性配位配体和单体可插入的任何其它部分; n等于0,1或2.在本发明的第二工艺步骤中，烯烃单体在聚合条件下与活化的催化剂组合物接触。

    Thermally reversible copolymers and process for the preparation thereof
    9.
    发明授权
    Thermally reversible copolymers and process for the preparation thereof 失效
    热可逆共聚物及其制备方法

    公开(公告)号：US4373068A

    公开(公告)日：1983-02-08

    申请号：US303219

    申请日：1981-09-18

    申请人： Binnur Gunesin ,  Gary R. Hamed ,  Jung W. Kang ,  Donald N. Schulz

    发明人： Binnur Gunesin ,  Gary R. Hamed ,  Jung W. Kang ,  Donald N. Schulz

    IPC分类号： C08F8/42 ,  C08F236/04 ,  C08L9/06 ,  C08L33/24

    CPC分类号： C08F236/04 ,  C08F8/42 ,  C08L9/06 ,  C08K3/0016

    摘要： The invention disclosed herein provides a novel thermally reversible copolymer having up to about 11 percent by weight of an N-(alkoxymethyl)acrylamide, a diene-containing synthetic rubber and a metal. The thermally reversible copolymer can be blended with conventional styrene-butadiene rubbers to improve the green strength thereof. Also disclosed herein is a process for improving the green strength of styrene-butadiene rubber which includes the steps of charging a reaction vessel with water, an emulsifier, an initiator, an N-(alkoxymethyl)acrylamide monomer and a vinyl monomer where one is desired, purging the vessel with an inert gas, charging a diene monomer and an activator to the reaction vessel, polymerizing the monomers to form a colymer latex, coagulating the latex with an aqueous metal salt to form a thermally reversible polymer and compounding the thermally reversible polymer with styrene-butadiene rubber.

    摘要翻译： 本文公开的本发明提供了具有高达约11重量％的N-（烷氧基甲基）丙烯酰胺，含二烯的合成橡胶和金属的新型热可逆共聚物。 热可逆共聚物可与常规丁苯橡胶共混以改善其生坯强度。 本文还公开了一种改善苯乙烯 - 丁二烯橡胶的生坯强度的方法，其包括以下步骤：向反应容器中加入水，乳化剂，引发剂，N-（烷氧基甲基）丙烯酰胺单体和乙烯基单体，其中需要一种 用惰性气体吹扫容器，将二烯单体和活化剂装入反应容器中，聚合单体以形成共聚物胶乳，用金属盐水溶液凝结胶乳以形成热可逆聚合物，并将热可逆聚合物 与丁苯橡胶。

    Thermally reversible copolymers and process for the preparation thereof
    10.
    发明授权
    Thermally reversible copolymers and process for the preparation thereof 失效
    热可逆共聚物及其制备方法

    公开(公告)号：US4307210A

    公开(公告)日：1981-12-22

    申请号：US132737

    申请日：1980-03-24

    申请人： Binnur Gunesin ,  Gary R. Hamed ,  Jung W. Kang ,  Donald N. Schulz

    发明人： Binnur Gunesin ,  Gary R. Hamed ,  Jung W. Kang ,  Donald N. Schulz

    IPC分类号： C08F8/42 ,  C08F8/00 ,  C08F8/44

    CPC分类号： C08F8/42

    摘要： The invention disclosed herein provides a novel thermally reversible copolymer having up to about 11 percent by weight of an N-(alkoxymethyl)acrylamide, a diene-containing synthetic rubber and a metal. The thermally reversible copolymer can be blended with conventional styrene-butadiene rubbers to improve the green strength thereof. Also disclosed herein is a process for improving the green strength of styrene-butadiene rubber which includes the steps of charging a reaction vessel with water, an emulsifier, an initiator, an N-(alkoxymethyl)acrylamide monomer and a vinyl monomer where one is desired, purging the vessel with an inert gas, charging a diene monomer and an activator to the reaction vessel, polymerizing the monomers to form a copolymer latex, coagulating the latex with an aqueous metal salt to form a thermally reversible polymer and compounding the thermally reversible polymer with styrene-butadiene rubber.

    摘要翻译： 本文公开的本发明提供了具有高达约11重量％的N-（烷氧基甲基）丙烯酰胺，含二烯的合成橡胶和金属的新型热可逆共聚物。 热可逆共聚物可与常规丁苯橡胶共混以改善其生坯强度。 本文还公开了一种改善苯乙烯 - 丁二烯橡胶的生坯强度的方法，其包括以下步骤：向反应容器中加入水，乳化剂，引发剂，N-（烷氧基甲基）丙烯酰胺单体和乙烯基单体，其中需要一种 用惰性气体吹扫容器，将二烯单体和活化剂装入反应容器中，聚合单体以形成共聚物胶乳，用金属盐水溶液凝结胶乳以形成热可逆聚合物，并将热可逆聚合物 与丁苯橡胶。