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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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2.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：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：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：US4120883A
公开(公告)日：1978-10-17
申请号：US750303
申请日：1976-12-13
CPC分类号： C08F10/00 , C07F3/02 , C07F5/066 , C07F7/0836 , C07F7/0896 , Y10S526/909
摘要： A method for producing an organomagnesium complex which is soluble in an inert hydrocarbon medium and expressed by the general formula Mg.sub..alpha. Al.sub..beta. R.sup.1 .sub.p Y.sub.q is provided. In this formula.alpha., .beta., p and q each is a number greater than zero,.alpha./.beta. = about 0.5 to 20,2.alpha. and 3.beta. = p + q,q/.beta. = about 0.5 to 1.5,Y is OR.sup.2 or OSiR.sup.3 R.sup.4 R.sup.5,R.sup.1, r.sup.2 and R.sup.3 each independently is a hydrocarbon radical having 1 to 20 carbon atoms, andR.sup.4 and R.sup.5 each independently is a hydrocarbon radical having 1 to 20 carbon atoms, hydrogen or a halogen atom.Said complex is prepared by reacting (A) an organomagnesium compound R.sup.1.sub.a M.sub.g X.sub.2-a wherein x is halogen, with (B) an aluminum compound AlYX.sub.2 wherein Y and X have the same meanings as above-defined. This method is superior to the prior art with respect to ease of reaction, high reaction efficiency and safety. Further the complex is safe during storage and handling. When the complex is employed as an olefin polymerization catalyst, the catalyst efficiency is higher and the characteristic properties of the resultant polymer are superior to those of polymers with other complexes.
摘要翻译： 提供了一种可溶于惰性烃介质并由通式MgαAlβR1 pYq表示的有机镁络合物的制备方法。 在这个公式中，alpha，β，P和Q每个数字大于零，alpha / beta =约0。
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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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9.发明授权Olefin polymerization catalyst and a process for producing polyolefins by the use of said catalyst 失效烯烃聚合催化剂和通过使用所述催化剂生产聚烯烃的方法
公开(公告)号：US4387045A
公开(公告)日：1983-06-07
申请号：US269062
申请日：1981-04-01
CPC分类号： C08F10/00
摘要： An olefin polymerization catalyst comprising a solid catalyst (I) and an organometallic compound (II), wherein said solid catalyst (I) is obtainable by reacting an organomagnesium compound (a) soluble in hydrocarbon solvent and represented by the following formula:MgR.sup.1.sub.p R.sup.2.sub.q X.sub.r(in the formula, R.sup.1 and R.sup.2, identical or different, represent a secondary or tertiary alkyl group having 4-6 carbon atoms, X represents a negative group containing O, N or S atom, p and q represent a number of 0-2, r represents a number of 0-1, and p, q and r satisfy: p+q+r=2) with a compound of titanium or vanadium having at least one halogen atom (b), has a high activity, is uniform, has a high density, is suitable for continuous polymerization of olefins, and enables to omit the catalyst removal step after the polymerization reaction.An olefin polymerization catalyst obtainable by replacing the solid catalyst (I) with a solid type catalyst (I') obtainable by further reacting solid catalyst (I) with compound (b) or with an organic or inorganic compound of aluminum, silicon, tin or antimony (c), and catalysts obtainable by adding a halogenated hydrocarbon (III) to the above-mentioned olefin polymerization catalysts give polyolefins having a broad molecular weight distribution.
摘要翻译： PCT No.PCT / JP79 / 00203 Sec。 371日期：1981年4月1日 102（e）1981年3月30日PCT PCT日期为1979年8月1日。包含固体催化剂（I）和有机金属化合物（II）的烯烃聚合催化剂，其中所述固体催化剂（I）可通过使有机镁 化合物（a）可溶于烃溶剂，由下式表示：MgR1pR2qXr（式中，R1和R2相同或不同，表示具有4-6个碳原子的仲或叔烷基，X表示含有O ，N或S原子，p和q表示0-2的数，r表示0-1的数，p，q和r满足：p + q + r = 2），钛或钒的化合物具有 至少一个卤素原子（b）具有高活性，均匀的，具有高密度，适用于烯烃的连续聚合，并且能够省去聚合反应后的催化剂除去步骤。 通过将固体催化剂（I）与化合物（b）进一步反应或与铝，硅，锡的有机或无机化合物反应获得的固体催化剂（I'）代替固体催化剂（I）得到的烯烃聚合催化剂， 锑（c）和通过向上述烯烃聚合催化剂中加入卤代烃（III）得到的催化剂得到具有宽分子量分布的聚烯烃。
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公开(公告)号：US4159965A
公开(公告)日：1979-07-03
申请号：US836343
申请日：1977-09-26
申请人： Hisaya Sakurai , Hideo Morita , Tadashi Ikegami , Shigeo Tsuyama
发明人： Hisaya Sakurai , Hideo Morita , Tadashi Ikegami , Shigeo Tsuyama
CPC分类号： C08F10/00
摘要： A catalyst useful for polymerizing olefins, capable of providing an extremely high catalyst efficiency, excellent grain size and high bulk density of polymer; production of polymer having various molecular weight distributions from a broader range to a narrower range and controlling of die swell of formed polymer, by using a mechanical grinding and contacting means. Said catalyst shows a high activity and higher stereoregularity in the polymerization of polypropylene when it is used together with an electron donor compound.Said catalyst comprises a solid catalyst component (A) and an organometallic compound (B), said catalyst component (A) is obtained by reacting a specified organomagnesium component (i) with a specified chlorosilane compound (ii) and reacting and/or grinding-contacting the solid obtained by the reaction of (i) and (ii) with a titanium and/or vanadium compound containing at least one halogen atom.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.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： 用于聚合烯烃的催化剂，能够提供极高的催化剂效率，优异的晶粒尺寸和高的聚合物堆积密度; 通过使用机械研磨和接触方法生产具有从较宽范围到较窄范围的各种分子量分布的聚合物和控制形成的聚合物的模头膨胀。 当与电子给体化合物一起使用时，所述催化剂在聚丙烯的聚合中显示出高活性和更高的立构规整性。
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