公开(公告)号：US4668753A

公开(公告)日：1987-05-26

申请号：US899796

申请日：1986-08-25

申请人： Norio Kashiwa ,  Mamoru Kioka ,  Masaki Kohyama ,  Masanobu Ishiyama

发明人： Norio Kashiwa ,  Mamoru Kioka ,  Masaki Kohyama ,  Masanobu Ishiyama

IPC分类号： C08F210/06 ,  C08F210/16 ,  C08J5/18 ,  C08F10/06

CPC分类号： C08J5/18 ,  C08F210/06 ,  C08F210/16 ,  C08J2323/16

摘要： A film-forming propylene copolymer composed of a major amount of propylene and a minor amount of ethylene, characterized by having(A) an ethylene content (Ec) of from 0.1 mole % to 2.0 mole % based on the total amount of propylene and ethylene, and(B) an isotactic value (Iso) in the range represented by the following formula (1) or (2),(i) when 0.1.ltoreq.Ec.ltoreq.0.3,Iso.gtoreq.-5Ec30 96.3 (%) (1),and(ii) when 0.3

摘要翻译： 由主要量的丙烯和少量乙烯组成的成膜丙烯共聚物，其特征在于（A）乙烯含量（Ec）为丙烯和乙烯的总量的0.1摩尔％至2.0摩尔％ ，和（B）当由下式（1）或（2）表示的范围内的全同立构度值（Iso）：（i）当0.1≤Eu≤0.3时，Iso> = -5_E + 96.3（ ％）（1）和（ii）当0.3 / = - 0.67_E + 95.0（％）（2）其中_E表示Ec（摩尔％）的数值; 共聚物膜; 以及该膜的制造方法。

公开(公告)号：US4742139A

公开(公告)日：1988-05-03

申请号：US6305

申请日：1987-01-15

申请人： Mamoru Kioka ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  C08F4/02 ,  C08F4/60 ,  C08F4/64 ,  C08F10/00

CPC分类号： C08F10/00

摘要： In a process for producing olefin polymer or copolymer by using a catalyst composed of (A) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor and derived from a magnesium-containing solid carrier obtained by contacting a magnesium compound in the liquid state with a precipitant, and (B) an organometallic compound of a metal selected from the group consisting of metals of Groups I to III of the periodic table; the improvement wherein(I) said catalyst component (A) is a reaction product of (iv) a titanium compound in the liquid state and a magnesium-containing solid carrier formed by contacting(i) a magnesium compound in the liquid state having no reducing ability and not containing a tetraalkoxy-, tetracycloalkoxy- or tetraaryloxy-titanium compound, said magnesium compound being selected from the specified group, with(ii) a precipitant other than a titanium compound, in the presence or absence of (iii) an electron donor having no active hydrogen, and(II) said reaction product is formed by reacting the titanium compound (iv) in the liquid state and the magnesium-containing solid carrier pre-treated or not-pre-treated with the electron donor (iii) having no active hydrogen in the presence or absence of the electron donor (iii) having no active hydrogen, the electron donor (iii) having no active hydrogen being used at least once in (I) and (II) above.

摘要翻译： 在通过使用由（A）含有镁，钛，卤素和电子给体的固体钛催化剂组分的催化剂制备烯烃聚合物或共聚物的方法中，该催化剂组分由镁化合物 具有沉淀剂的液态，和（B）选自元素周期表第I至III族金属的金属的有机金属化合物; 其中（I）所述催化剂组分（A）是（iv）液态钛化合物与通过使（i）不具有还原性的液态的镁化合物接触而形成的含镁固体载体的反应产物 并且不含四烷氧基，四环烷氧基或四芳氧基钛化合物，所述镁化合物选自指定基团，（ii）除钛化合物以外的沉淀剂，在（iii）电子给体 没有活性氢，和（II）所述反应产物是通过使液态的钛化合物（ⅳ）与预处理或未经预处理的含镁固体载体与电子给体（ⅲ）反应形成的，所述电子给体（ⅲ）具有 在没有活性氢的电子给体（iii）的存在或不存在下，没有活性氢，在上述（I）和（II）中不使用活性氢的电子给体（iii）至少一次。

公开(公告)号：US4401589A

公开(公告)日：1983-08-30

申请号：US322201

申请日：1981-11-17

申请人： Mamoru Kioka ,  Hiroaki Kitani ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Hiroaki Kitani ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  C08F4/02 ,  C08F4/44 ,  C08F4/60 ,  C08F4/64 ,  C08F10/00 ,  C08F10/04

CPC分类号： C08F10/00 ,  C08F4/022

摘要： Improved process for producing olefin polymer or copolymer characterized by using (I) a solid catalyst component (A) which is the product of reaction of (a) a magnesium compound in the liquid state having no reducing ability with (b) a titanium compound in the liquid state in the presence of an electron donor having no active hydrogen, said magnesium compound (a) being a liquid magnesium compound or a solution of a magnesium compound or being obtained by contacting the magnesium compound with at least one electron donor selected from the group consisting of alcohols, organic carboxylic acids, aldehydes, amines and mixtures thereof, or the product of reaction of the magnesium compound (a) with the titanium compound (b) in the absence of the electron donor having no active hydrogen atom followed by treatment with the electron donor having no active hydrogen atom, and (II) the mole ratio of the compound (a) to the compound (b), calculated as metal atoms, is at least about 2.

摘要翻译： 改进的制备烯烃聚合物或共聚物的方法，其特征在于使用（a）作为（a）不具有还原能力的液态镁化合物与（b）钛化合物的反应的产物的固体催化剂组分（A） 在没有活性氢的电子给体的存在下的液态，所述镁化合物（a）是液体镁化合物或镁化合物的溶液，或通过使镁化合物与至少一种电子给体接触而获得，所述电子给体选自 或由镁化合物（a）与钛化合物（b）在不存在不具有活性氢原子的电子给体存在下进行反应的反应产物，然后进行处理的产物如醇，有机羧酸，醛，胺及其混合物 电子给体不具有活性氢原子，和（II）以金属原子计算的化合物（a）与化合物（b）的摩尔比为至少约2。

公开(公告)号：US4328328A

公开(公告)日：1982-05-04

申请号：US100098

申请日：1979-12-04

申请人： Syuji Minami ,  Takashi Ueda ,  Mamoru Kioka ,  Norio Kashiwa

发明人： Syuji Minami ,  Takashi Ueda ,  Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  C08F4/02 ,  C08F4/60 ,  C08F4/62 ,  C08F4/639 ,  C08F4/64 ,  C08F10/00 ,  C08F10/02

CPC分类号： C08F10/00 ,  C08F4/022

摘要： In a continuous process for producing a polymer or copolymer of an alpha-olefin in a hydrocarbon solvent in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound, the improvement wherein[I] polymerization or copolymerization is carried out in the presence of a catalyst composed of(A) a magnesium compound in the liquid state which is soluble in said hydrocarbon solvent and is free from an organoaluminum compound and a transition metal compound, said magnesium compound being obtained from specific reactants,(B) a transition metal compound in the liquid state, and(C) an organoaluminum compound, and[II] said polymerization or copolymerization is carried out while feeding said compound (C) into a polymerization or copolymerization zone separately from said other compounds (A) and (B), or while adding a part or the whole of said compound (C) to a liquid mixture of said other compounds (A) and (B) and feeding the resulting mixture into said zone, or while feeding a mixture of the compounds (A), (B) and (C) into said zone.

摘要翻译： 在包含过渡金属化合物和有机铝化合物的催化剂存在下，在烃溶剂中制备α-烯烃的聚合物或共聚物的连续方法中，其中[I]聚合或共聚在存在下进行 由（A）液态的镁化合物（其可溶于所述烃溶剂并且不含有机铝化合物和过渡金属化合物）组成的催化剂，所述镁化合物由特定反应物获得，（B）过渡金属 以及（C）有机铝化合物，和[II]在将所述化合物（C）与所述其它化合物（A）和（B）分开地进入聚合或共聚区的同时进行聚合或共聚， 或者将所述化合物（C）的一部分或全部添加到所述其它化合物（A）和（B）的液体混合物中，并将所得混合物进料到所述区域 或者将化合物（A），（B）和（C）的混合物进料到所述区域中。

公开(公告)号：US5583188A

公开(公告)日：1996-12-10

申请号：US229104

申请日：1994-04-18

申请人： Norio Kashiwa ,  Mamoru Kioka ,  Yoshihisa Ushida

发明人： Norio Kashiwa ,  Mamoru Kioka ,  Yoshihisa Ushida

IPC分类号： C08F4/00 ,  C08F4/60 ,  C08F4/62 ,  C08F4/64 ,  C08F10/00 ,  C08F4/651 ,  C08F4/654

CPC分类号： C08F10/00

摘要： As improved process for producing an olefin polymer or copolymer by using a novel catalyst composition composed of (A) a titanium catalyst component containing magnesium, titanium, halogen and an ester specified in claim 1, as an electron donor, (B) an organoaluminum compound and (C) a heterocyclic compound or a ketone specified in claim 1, as a third component. The combination parameter of the ester in (A) and the (C) component is new, and the process can give a highly stereospecific olefin polymer or copolymer in high yields.

摘要翻译： 作为通过使用由（A）包含镁，钛，卤素和权利要求1所定义的酯的钛催化剂组分构成的新的催化剂组合物作为电子给体，（B）有机铝化合物 和（C）权利要求1所述的杂环化合物或酮作为第三成分。 （A）和（C）组分中的酯的组合参数是新的，并且该方法可以以高产率产生高度立体有择的烯烃聚合物或共聚物。

公开(公告)号：US5028671A

公开(公告)日：1991-07-02

申请号：US430081

申请日：1989-11-01

申请人： Mamoru Kioka ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/64 ,  C08F4/646 ,  C08F10/00

CPC分类号： C08F10/00 ,  Y10S526/904

摘要： A catalyst formed from(A) a solid titanium catalyst component containing magnesium, titanium, halogen and a polycarboxylic acid ester as essential ingredients and being obtained by contacting a magnesium compound, a titanium compound and a polycarboxylic acid ester,(B) an organoaluminum compound, and(C) an organosilicon compound represented by the following formula (1)SiR.sup.1 R.sup.2 (OR.sup.3).sub.2 (1) wherein R.sup.1 is selected from the class consisting of linear alkyl groups having at least 3 carbon atoms and arylalkyl groups in which the alkyl moiety has a secondary or tertiary alpha-carbon atom, R.sup.2 is selected from the class consisting of alkyl groups and arylalkyl groups in which the alkyl moiety has a secondary or tertiary alpha-carbon atom, and R.sup.3 is a hydrocarbon group, with the proviso that when R.sup.1 is a linear alkyl group having at least 3 carbon atoms and R.sup.2 is an alkyl group, the alkyl group for R.sup.2 is a linear alkyl group having at least 3 carbon atoms,and process for production thereof.

公开(公告)号：US4370455A

公开(公告)日：1983-01-25

申请号：US101470

申请日：1979-12-10

申请人： Takashi Ueda ,  Syuji Minami ,  Mamoru Kioka ,  Norio Kashiwa

发明人： Takashi Ueda ,  Syuji Minami ,  Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  C08F4/60 ,  C08F10/00 ,  C08F4/02

CPC分类号： C08F10/00

摘要： In a process for producing a polymer or copolymer of an alpha-olefin which comprises continuously polymerizing or copolymerizing the alpha-olefin or the alpha-olefin with up to 5 mole % of a diolefin in the presence of a catalyst comprising a transition metal catalyst component and an organoaluminum catalyst component, the improvement wherein:(I) said polymerization or copolymerization is carried out in the presence of a catalyst composed of (A) a solid magnesium compound obtained by reacting (i) an adduct between a magnesium halide and an electron donor, with (ii) an organometallic compound of a metal of Groups I to III of the Mendelejeff's periodic table, (B) a liquid transition metal compound, and (C) an organoaluminum compound, and(II) said continuous polymerization or copolymerization is carried out while feeding the compound (B) separately from the other compounds (A) and (C) into a polymerization or copolymerization zone.

摘要翻译： 在制备α-烯烃的聚合物或共聚物的方法中，其包括在包含过渡金属催化剂组分的催化剂存在下，使α-烯烃或α-烯烃与至多5摩尔％的二烯烃连续聚合或共聚 和有机铝催化剂组分的改进，其中：（I）所述聚合或共聚在催化剂存在下进行，所述催化剂由（A）通过（i）卤化镁和电子之间的加合物反应获得的固体镁化合物 （ii）Mendelejeff周期表第I至III族金属的有机金属化合物，（B）液体过渡金属化合物和（C）有机铝化合物，和（II）所述连续聚合或共聚是 在将化合物（B）与其它化合物（A）和（C）分开地进料到聚合或共聚区中的同时进行。

公开(公告)号：US4330649A

公开(公告)日：1982-05-18

申请号：US159440

申请日：1980-06-13

申请人： Mamoru Kioka ,  Hiroaki Kitani ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Hiroaki Kitani ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  C08F4/02 ,  C08F4/44 ,  C08F4/60 ,  C08F4/64 ,  C08F10/00 ,  C08F10/04

CPC分类号： C08F10/00 ,  C08F4/022

摘要： Improved process for producing olefin polymer or copolymer characterized by using (I) a solid catalyst component (A) which is he product of reaction of (a) a magnesium compound in the liquid state having no reducing ability with (b) a titanium compound in the liquid state in the presence of an electron donor having no active hydrogen, said magnesium compound (a) being a liquid magnesium compound or a solution of a magnesium compound or being obtained by contacting the magnesium compound with at least one electron donor selected from the group consisting of alcohols, organic carboxylic acids, aldehydes, amines and mixtures thereof, or the product of reaction of the magnesium compound (a) with the titanium compound (b) in the absence of the electron donor having no active hydrogen atom followed by treatment with the electron donor having no active hydrogen atom, and (II) the mole ratio of the compound (a) to the compound (b), calculated as metal atoms, is at least about 2.

摘要翻译： 改进的制备烯烃聚合物或共聚物的方法，其特征在于使用（I）作为（a）不具有还原能力的液态的镁化合物与（b）钛化合物的反应的固体催化剂组分（A） 在没有活性氢的电子给体的存在下的液态，所述镁化合物（a）是液体镁化合物或镁化合物的溶液，或通过使镁化合物与至少一种电子给体接触而获得，所述电子给体选自 或由镁化合物（a）与钛化合物（b）在不存在不具有活性氢原子的电子给体存在下进行反应的反应产物，然后进行处理的产物如醇，有机羧酸，醛，胺及其混合物 电子给体不具有活性氢原子，和（II）以金属原子计算的化合物（a）与化合物（b）的摩尔比为至少约2。

公开(公告)号：US4952649A

公开(公告)日：1990-08-28

申请号：US169171

申请日：1988-03-11

申请人： Mamoru Kioka ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/00 ,  B01J31/14 ,  B01J37/04 ,  C08F4/02 ,  C08F4/06 ,  C08F4/10 ,  C08F4/12 ,  C08F4/16 ,  C08F4/60 ,  C08F4/64 ,  C08F4/654 ,  C08F4/658 ,  C08F10/00 ,  C08F10/04

CPC分类号： C08F10/00 ,  Y10S526/904 ,  Y10S526/909

摘要： A solid titanium catalyst component (A) of a catalyst system useful in the polymerization of olefins or copolymerization of two or more olefins or one or more olefins and a diene is prepared by contacting a liquid hydrocarbon solution of (i) a magnesium compound, such as magnesium chloride, with (ii) a liquid titanium compound, such as TiCl.sub.4, or a solution of a titanium compound in a hydrocarbon solvent, to form a solid product. The solid product is formed in the presence of (D) an electron donor, e.g. methyl formate, acetic acid, acetic anhydride, acetone, methyl ether, butyl Cellosolve, dimethyl carbonate, methyl silicate. The solid product is also contacted with a polycarboxylic acid ester, e.g. diethyl methylsuccinate. The polymerization or copolymerization of the olefin is carried out in the presence of the solid titanium catalyst (A) and (B) an organometallic compound of a Group I to III metal and (C) an organic silicon compound having an Si--O--C bond. Granular or spherical polyethylene, polypropylene, poly(butene-1), poly(4-methylpentene-1), etc. are produced in high yield, with good flowability, high bulk density, and narrow particle size distribution. The polymers can be produced over a wide range of melt index values without reduction in stereospecificity. Catalyst activity is retained with passage of time.

摘要翻译： 通过使（ⅰ）镁化合物的液体烃溶液（例如镁）与其它烯烃和二烯烃的液体烃溶液接触，制备可用于烯烃聚合或两种或多种烯烃或一种或多种烯烃和二烯的共聚合的催化剂体系的固体钛催化剂组分（A） 与（ii）液体钛化合物如TiCl 4或钛化合物在烃溶剂中的溶液形成固体产物。 在（D）电子给体的存在下形成固体产物，例如 甲酸甲酯，乙酸，乙酸酐，丙酮，甲基醚，丁基溶纤剂，碳酸二甲酯，硅酸甲酯。 固体产物也与多元羧酸酯例如， 甲基琥珀酸二乙酯 烯烃的聚合或共聚在固体钛催化剂（A）和（B）I至III族金属的有机金属化合物和（C）具有Si-O-C键的有机硅化合物的存在下进行。 以高产率，良好的流动性，高堆积密度和窄的粒度分布产生颗粒或球形聚乙烯，聚丙烯，聚（丁烯-1），聚（4-甲基戊烯-1）等。 聚合物可以在宽范围的熔体指数值下生产而不降低立体定向性。 催化剂活性随着时间的推移而保持。

公开(公告)号：US4923833A

公开(公告)日：1990-05-08

申请号：US245400

申请日：1988-08-23

申请人： Mamoru Kioka ,  Norio Kashiwa

发明人： Mamoru Kioka ,  Norio Kashiwa

IPC分类号： C08F4/60 ,  C08F4/64 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00

CPC分类号： C08F10/00 ,  C08F4/65925 ,  Y10S526/904 ,  Y10S526/943

摘要： The solid catalyst of this invention for olefin polymerization comprises a compound of a transition metal of Group IV of the periodic table and an aluminoxane as catalyst ingredients. The catalyst is characteristic in that it has a high specific surface area, and shows very high polymerization activity on the homopolymerization or copolymerization of olefins. Polymers obtained by using the catalyst of the invention have a high bulk density, a uniform particle size, a low fine powder content and a narrow molecular weight distribution, and in the case of copolymers, a narrow composition distribution as well.