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1.发明授权
公开(公告)号：US4159256A
公开(公告)日：1979-06-26
申请号：US876823
申请日：1978-02-10
CPC分类号： C08F10/00
摘要： Novel high active catalysts useful for highly stereospecific polymerization of olefin which enables to produce polymer of low content of catalyst residue, and of good grain size having a high stereoregularity can be obtained by a combination of [A] a solid catalyst component obtained by reacting and/or grinding a specified organomagnesium component (i) with a specified chlorosilane compound containing Si-H (ii) to obtain a solid (1) and reacting said solid (1) with a titanium compound containing at least one halogen atom (2) and a carboxylic acid or a derivative thereof (3) and [B] a component consisting of an organometallic compound and a carboxylic acid or a derivative thereof. The organomagnesium component is of the formulaM.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.swherein .alpha. is a number of 0 or greater than 0; .beta.>0, p, q, r, and s are each a number of 0 or greater; p+q+r+s=m.alpha.+2.beta. wherein m is the valency of M; M is a metal element of the 1st to the 3rd group of the Periodic Table; R.sup.1 and R.sup.2 are the same or different hydrocarbon radicals having 1 to 20 carbon atoms; X and Y are the same or different radicals selected from the group consisting of halogen, OR.sup.3, OSiR.sup.4 R.sup.5 R.sup.6, NR.sup.7 R.sup.8 and SR.sup.9 wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen atom or a hydrocarbon radical having 1 to 20 carbon atoms and R.sup.9 is a hydrocarbon radical having 1 to 20 carbon atoms, and chlorosilane is of the formulaH.sub.a SiCl.sub.b R.sub.4-(a+b)wherein a and b are each a number greater than 0, having the relationships a.ltoreq.2 and a+b.ltoreq.4 wherein R is a hydrocarbon radical having 1 to 20 carbon atoms.
摘要翻译： 可以通过将[A]通过反应获得的固体催化剂组分与通式（1）所得的固体催化剂组分的组合，得到可用于烯烃的高立体特异性聚合的新型高活性催化剂，其能够生产低含量催化剂残余物和具有高立构规整性的良好晶粒尺寸的聚合物， /或用指定的含有Si-H（ⅱ）的氯代硅烷化合物研磨指定的有机镁组分（ⅰ），得到固体（1），并使所述固体（1）与含有至少一个卤素原子（2）和 羧酸或其衍生物（3）和[B]由有机金属化合物和羧酸或其衍生物组成的组分。 有机镁组分的分子式为MαMgβRp1Rq2XrYs，其中α为0或大于0; β> 0，P，Q，R和S是每个0或更大的数目; P + Q + R + S = Mα+ 2β，其中M是M的值; M是周期表第1至第3组的金属元素; R1和R2是相同或不同的具有1至20个碳原子的烃基; X和Y是选自卤素，OR 3，OSiR 4 R 5 R 6，NR 7 R 8和SR 9中相同或不同的基团，其中R 3，R 4，R 5，R 6，R 7和R 8各自为氢原子或具有1至20个碳原子的烃基 并且R 9是具有1至20个碳原子的烃基，并且氯代硅烷具有式HaSiClbR 4 - （a + b）。其中A和B在每个大于0的数字之间，具有相关性A
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公开(公告)号：US4526941A
公开(公告)日：1985-07-02
申请号：US535459
申请日：1983-09-23
CPC分类号： C08F10/00
摘要： A process for polymerizing an .alpha.-olefin which comprises contacting the .alpha.-olefin at a temperature of about 10.degree. C. to about 100.degree. C. with a catalyst comprising a slurry component (A) and an organometallic component (B), the component (A) being obtained, without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formulaM.alpha.Mg.beta.R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.sor of the reaction product of M.alpha.Mg.beta.R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formulaH.sub.a SiCl.sub.b R.sub.4-(a+b).sup.10at a temperature of about 20.degree. C. to about 150.degree. C., with (2) a titanium compound of the formulaTi(OR.sup.11).sub.n Z.sub.4-nand (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
摘要翻译： 一种聚合α-烯烃的方法，其包括在约10℃至约100℃的温度下与包含淤浆组分（A）和有机金属组分（B）的催化剂接触所述α-烯烃，所述组分 （A）通过使（1）通过使一摩尔（i）通式MαMgβR p 1 R q 2 X r Y的烃可溶性有机镁组分或反应生成的浆料反应混合物而获得，无中间或最终固体分离， 具有选自醚，硫醚，酮，醛，羧酸或其衍生物，醇，硫代醇和胺的至少一种电子给体的MαMgβRp1Rq2XrY的产物与0.1至10摩尔的（ⅱ）氯硅烷 在约20℃至约150℃的温度下，式（II）的化合物式为：H 1 Cl b R 4 - （a + b）10）与（2）式Ti（OR 11）n Z 4-n的钛化合物和（3） 含氮或含硫杂环羧酸 酸酯或烃基羧酸酯，（2）钛化合物/（3）羧酸酯的摩尔比至少为0.3。
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公开(公告)号：US4255280A
公开(公告)日：1981-03-10
申请号：US19674
申请日：1979-03-12
CPC分类号： C08F10/00
摘要： Catalysts for polymerization of olefin which comprise a solid catalyst component (A) and an organometallic compound with a heterocyclic carboxylic acid ester (B), wherein the solid catalyst component (A) is obtained by reacting or/and grinding an organomagnesium compound (1), of the formulaM.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.rwherein.alpha., p, q and r each independently .gtoreq.0,.beta.>0,p+q+r=m.alpha.+2.beta.M is Al, Zn, B or Be,m is the valence of M,R.sup.1 and R.sup.2 are the same or different hydrocarbon groups having 1-20 carbon atoms, andX is a halogen atom,or of the reaction product of M.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r with an electron donor, with 0.01 to 100 moles of (ii) a chlorosilane compound containing Si-H bonds and of the formulaH.sub.a SiClR.sub.4-(a+b).sup.3wherein0
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公开(公告)号：US4330650A
公开(公告)日：1982-05-18
申请号：US135069
申请日：1980-03-28
CPC分类号： C08F10/00
摘要： Catalysts for polymerization of olefin which comprise a solid catalyst component (A) and an organometallic compound with a heterocyclic carboxylic acid ester (B), wherein the solid catalyst component (A) is obtained by reacting or/and grinding a special magnesium compound (1), a titanium halide (2) and a carboxylic acid ester (3); and the heterocyclic carboxylic acid ester is N-, S- or O-containing heterocyclic compound, and processes for polymerization of olefin employing such a catalyst.
摘要翻译： 用于使包含固体催化剂组分（A）和带有杂环羧酸酯（B）的有机金属化合物的烯烃聚合的催化剂，其中固体催化剂组分（A）通过使特殊的镁化合物（1） ），卤化钛（2）和羧酸酯（3）; 并且杂环羧酸酯是含有N-，S-或O-的杂环化合物，以及使用这种催化剂聚合烯烃的方法。
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公开(公告)号：US4159963A
公开(公告)日：1979-07-03
申请号：US873630
申请日：1978-01-30
申请人： Hisaya Sakurai , Hideo Morita , Tadashi Ikegami , Masayoshi Miya
发明人： Hisaya Sakurai , Hideo Morita , Tadashi Ikegami , Masayoshi Miya
CPC分类号： C08F10/00
摘要： Novel highly active catalysts useful for highly stereospecific polymerization of olefin which enables to produce polymer of good grain size having a high stereoregularity can be obtained by a combination of [A] a solid catalyst component obtained by reacting a specified organomagnesium component (i) with a specified chlorosilane compound containing Si--H (ii) to obtain a solid (1) and reacting said solid (1) with a titanium compound containing at least one halogen atom (2) and a carboxylic acid or a derivative thereof (3) and [B] a component consisting of an organometallic compound and a carboxylic acid or a derivative thereof.The organomagnesium component is of the formulaM.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.swherein .alpha. is a number of 0 or greater than 0; .beta.> 0; p, q, r and s are each a number of 0 or greater; p+q+r+s=m.alpha.+2.beta. wherein m is the valency of M; M is a metal element of the 1st to the 3rd group of the Periodical Table; R.sup.1 and R.sup.2 are the same or different hydrocarbon radicals having 1 to 20 carbon atoms; X and Y are the same or different radicals selected from the group consisting of halogen, OR.sub.3, OSiR.sup.4 R.sup.5 R.sup.6, NR.sup.7 R.sup.8 and SR.sup.9 wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen atom or a hydrocarbon radical having 1 to 20 carbon atoms and R.sup.9 is a hydrocarbon radical having 1 to 20 carbon atoms,And chlorosilane is of the formulaH.sub.a SiCl.sub.b R.sub.4-(a+b)wherein a and b are each a number greater than 0, having the relationship a.ltoreq.2 and a+b.ltoreq.4 wherein R is a hydrocarbon radical having 1 to 20 carbon atoms.
摘要翻译： 可以通过组合使用[A]将特定的有机镁成分（i）与（a）成分反应而得到的固体催化剂成分与[A]的组合，得到可用于烯烃的高立体特异性聚合的高活性催化剂，其能够制备具有高立构规整度的良好粒径的聚合物 含有Si-H（ii）的指定的氯硅烷化合物以获得固体（1），并使所述固体（1）与含有至少一个卤素原子（2）和羧酸或其衍生物（3）的钛化合物和 B]由有机金属化合物和羧酸或其衍生物组成的组分。
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公开(公告)号：US4312783A
公开(公告)日：1982-01-26
申请号：US169234
申请日：1980-07-16
CPC分类号： C08F10/00
摘要： A catalyst comprising (A) a solid catalyst component obtained by reacting a titanium compound having a hydrocarbyloxy group with an organoaluminum compound in the presence of an ether to give a liquid material or to give a solid titanium component (a) which is solubilized by addition of a tetravalent titanium halide with or without an ether without separation or after separation from the reaction mixture, and heat treating the liquid material at a temperature of 70.degree. to 180.degree. C. with or without addition of a tetravalent titanium halide, and (B) an organoaluminum compound is effective for polymerization or copolymerization of olefins with high stereoregularity and has high polymerization activity.
摘要翻译： 一种催化剂，其包含（A）通过使具有烃氧基的钛化合物与有机铝化合物在醚存在下反应而获得的固体催化剂组分，得到液体材料或得到通过加成溶解的固体钛组分（a） 的四价钛卤化物，无需分离或不与反应混合物分离，并在70℃至180℃的温度下加热或不加入四价卤化钛，和（B ）有机铝化合物对于具有高立构规整性的烯烃的聚合或共聚有效，并且具有高聚合活性。
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7.发明授权Catalyst for polymerization of olefins and polymerization process employing such catalyst 失效用于烯烃聚合的催化剂和使用这种催化剂的聚合方法
公开(公告)号：US4431568A
公开(公告)日：1984-02-14
申请号：US331103
申请日：1981-12-15
申请人： Masayoshi Miya , Hisaya Sakurai , Tadashi Ikegami
发明人： Masayoshi Miya , Hisaya Sakurai , Tadashi Ikegami
CPC分类号： C08F10/00
摘要： A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) a solid inorganic oxide, (2) a hydrocarbon-soluble organomagnesium component of the general formulaM.sub..alpha. M.sub.g.beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.swherein.alpha., p, q, r and s each independently is 0 or a number greater than 0,.beta.is a number greater than 0,p+q+r+s=m.alpha.+2.beta.,m is the valence of M,M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 and R.sup.2 each independently is a hydrocarbon group having 1 to 20 carbon atoms,X and Y each independently is an OR.sup.3, OSiR.sup.4 R.sup.5 R.sup.6, NR.sup.7 R.sup.8 or SR.sup.9 group wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R.sup.9 is a hydrocarbon group having 1 to 20 carbon atoms,or of the reaction product of M.sub..alpha. M.sub.g.beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines and (3) a chlorosilane compound having a Si-H bond and of the formulaH.sub.a SiCl.sub.b R.sub.4-.sup.10 (a+b)whereinR.sup.10 is a hydrocarbon group having 1 to 20 carbon atoms,0 0 anda+b.ltoreq.4,separating a reaction product from the reaction mixture and washing the separated reaction product with an inert hydrocarbon and reacting the washed reaction product with (4) a titanium compound having at least one halogen atom and/or a vanadium compound having at least one halogen atom, and a polymerization process employing such a catalyst.
摘要翻译： 一种用于聚合烯烃的催化剂，其包含固体催化剂组分[A]和有机金属组分[B]，固体催化剂组分[A]是通过使（1）固体无机氧化物，（2）可溶于烃的有机镁 其中α，p，q，r和s各自独立地为0或大于0的数，β为大于0的数，p + q + r + s =mα+ 2β，m是M的化合价，M是元素周期表第1至第3族的金属，R 1和R 2各自独立地是具有1至20个碳原子的烃基，X和Y各自独立地是OR 3， OSiR 4 R 5 R 6，NR 7 R 8或SR 9基团，其中R 3，R 4，R 5，R 6，R 7和R 8各自独立地为氢原子或具有1至20个碳原子的烃基，R 9为具有1至20个碳原子的烃基， MαMgβRp1Rq2XrY与至少一种选自以下的电子给体的反应产物 醚，硫醚，酮，醛，羧酸或其衍生物，醇，硫代醇和胺，和（3）具有Si-H键和式IIaSiClbR4-10（a + b）的氯代硅烷化合物，其中R 10是烃 具有1至20个碳原子的烷基，0 0和a + b 4，将反应产物与反应混合物分离并用惰性烃洗涤分离的反应产物，并将洗涤的反应物 产物与（4）具有至少一个卤素原子的钛化合物和/或具有至少一个卤素原子的钒化合物，以及使用这种催化剂的聚合方法。
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公开(公告)号：US4027089A
公开(公告)日：1977-05-31
申请号：US579639
申请日：1975-05-21
申请人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
发明人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
CPC分类号： C08F10/00
摘要： A novel process for polymerizing ethylene or a mixture of ethylene and another olefin is provided. In this process a novel catalyst having a very high activity per solid component of catalyst is used. Said catalyst is prepared by reacting a specific hydrocarbon-soluble organoaluminum-magnesium complex containing alkoxy, aryloxy, siloxy or siloxane groups, with one or more kinds of a titanium or vanadium compound having at least one halogen atom, and subsequently reacting the thus obtained hydrocarbon-insoluble reaction product (A) with a specified organoaluminum compound (B).
摘要翻译： 提供了一种聚合乙烯或乙烯与另一种烯烃的混合物的新方法。 在该方法中，使用催化剂固体成分具有非常高的活性的新型催化剂。 所述催化剂是通过使具有烷氧基，芳氧基，甲硅烷氧基或硅氧烷基团的特定的可溶于烃的有机铝 - 镁络合物与一种或多种具有至少一个卤素原子的钛或钒化合物反应制备的，随后使由此得到的烃 - 不溶性反应产物（A）与指定的有机铝化合物（B）反应。
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公开(公告)号：US4004071A
公开(公告)日：1977-01-18
申请号：US569044
申请日：1975-04-17
申请人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
发明人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
CPC分类号： C08F10/00
摘要： Polyethylene or copolymers of ethylene with another .alpha.-olefin can be produced by the use of a novel polymerization catalyst obtained by using, in combination, (A) a specified, hydrocarbon-insoluble solid component prepared by reacting (i) a specific, hydrocarbon-soluble organoaluminum-magnesium complex (Al.sub.n Mg.sub.m R.sub.n(3.sub.-.sub..alpha.).sup.1 -R.sub.2m.sup.2 H.sub.n, wherein R.sup.1 and R.sup.2 are hydrocarbon radicals) with (ii) a titanium or vanadium compound containing halogen atom(s), and (B) an organoaluminum compound. This catalyst exhibits a surprisingly high activity per the unit amount of the solid component.
摘要翻译： 聚乙烯或乙烯与另一种α-烯烃的共聚物可以通过使用通过组合使用（A）特定的不溶于烃的固体组分获得的新型聚合催化剂来制备，所述固体组分通过使（i）特定的烃 - 可溶性有机铝 - 镁络合物（AlnMgmRn（3-α）1-R2m2Hn，其中R1和R2为烃基）与（ⅱ）含有卤原子的钛或钒化合物和（B）有机铝化合物。 该催化剂表现出每单位量的固体组分惊人的高活性。
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公开(公告)号：US3989878A
公开(公告)日：1976-11-02
申请号：US579752
申请日：1975-05-21
申请人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
发明人： Itsuho Aishima , Hisaya Sakurai , Yukichi Takashi , Hideo Morita , Tadashi Ikegami , Toshio Sato
摘要： A process for polymerizing ethylene or a mixture of ethylene and another olefin is proposed in which the polymerization can be carried out with an extremely high efficiency by using a catalyst prepared by reacting (A) a hydrocarbon-insoluble reaction product (obtained by reacting (i) a specified organomagnesium-containing hydrocarbon-soluble complex, or reaction product of (i), with (ii) a specified siloxane compound and with (iii) at least one kind of titanium or vanadium compound containing at least one halogen atom), with (B) a specified organoaluminum compound. Resultant polymers have a high molecular weight and a high rigidity and molecular weight and molecular weight distribution thereof can be easily controlled.
摘要翻译： 提出了一种使乙烯或乙烯与另一种烯烃的混合物聚合的方法，其中可以通过使用通过使（A）不溶于烃的反应产物（通过使（i ）指定的含有机镁的烃溶性络合物或（i）的反应产物与（ii）指定的硅氧烷化合物和（iii）至少一种含有至少一个卤素原子的钛或钒化合物的反应产物） （B）指定的有机铝化合物。 所得聚合物具有高分子量，并且可以容易地控制高刚性和分子量，并且其分子量分布。
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