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    • 1. 发明授权
    • Solid catalyst component for alpha-olefin polymerization and process for
producing same
    • 用于α-烯烃聚合的固体催化剂组分及其制备方法
    • US4591577A
    • 1986-05-27
    • US740999
    • 1985-06-04
    • Akihiro SatoMasami TachibanaHiroshi ShimizuToshihiro Uwai
    • Akihiro SatoMasami TachibanaHiroshi ShimizuToshihiro Uwai
    • C08F4/00C08F4/60C08F4/64C08F4/642C08F10/00
    • C08F10/00Y10S526/908Y10S526/909
    • A solid catalyst component for .alpha.-olefin polymerization which, when produced, causes any troubles due to its small particle size and when used, yields a spherical polymer of a suitably less particle size and a high bulk density with a slightest quantity of atactic polymer and affording a very good dispersibility of powdery additives therein in spite of its narrow particle size distribution, and a process for producing the same, are provided, which solid catalyst component comprises Ti and Cl as active ingredients, having an average particle diameter of 2 to 10.mu., a specific surface area of 100 m.sup.2 /g or more and a diffraction line corresponding to a distance between lattices of 4.80 to 5.10 .ANG. by way of X-ray diffraction; and which process is characterized in that when TiCl.sub.4 is reduced with a reducing agent comprising an organoaluminum compound to produce a solid intermediate, there is employed an agitation intensity defined by definite values of agitation power and baffle ratio.
    • 一种用于α-烯烃聚合的固体催化剂组分,其在制备时由于其小粒径而引起任何故障,并且当使用时,产生具有适度较小粒径和高堆积密度的球形聚合物,其中最少量的无规立构聚合物和 提供粉末状添加剂的分散性非常好,尽管其粒度分布窄,并且提供了其制备方法,该固体催化剂组分包含Ti和Cl作为活性成分,其平均粒径为2至10 mu,比表面积为100m 2 / g以上,通过X射线衍射对应于晶格之间的间距4.80〜5.10的衍射线; 并且该方法的特征在于,当用包含有机铝化合物的还原剂还原TiCl 4以产生固体中间体时,使用通过搅拌功率和挡板比的确定值定义的搅拌强度。
    • 3. 发明授权
    • Process for producing .alpha.-olefin polymers
    • 制备α-烯烃聚合物的方法
    • US4460757A
    • 1984-07-17
    • US403105
    • 1982-07-29
    • Akihiro SatoMasami TachibanaToshihiro UwaiKenji MatsudaYoshiharu Higuchi
    • Akihiro SatoMasami TachibanaToshihiro UwaiKenji MatsudaYoshiharu Higuchi
    • C08F4/00C08F2/00C08F4/60C08F4/64C08F10/00
    • C08F10/00Y10S526/904
    • A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.-olefin in the presence of the final solid product and (A.sub.2) to obtain another preactivated catalyst. The catalyst has a superior storage stability and heat stability.
    • 提供了一种以高产率生产具有良好颗粒形式的高结晶性α-烯烃聚合物的方法,其包括在通过使有机铝化合物(A1)的反应产物(I)与电子反应获得的预活化催化剂存在下聚合α-烯烃 (B1)与TiCl4得到固体产物(II); 进一步使(II)与电子给体(B2)和电子受体反应得到固体产物(III); 在用于获得(II)的反应步骤期间或/和/或在反应步骤中或/或之后获得(III),使(II)或(III)进行聚合处理的α-烯烃; 将得到的最终固体产物与有机铝化合物(A2)和有机铝化合物(A3)的反应产物(G)与电子给体(B3)合并,得到预活化催化剂; 并且优选地,在该组合中,在最终固体产物和(A2)的存在下,使一部分或全部催化剂进一步用α-烯烃进行聚合处理,以获得另一种预活化的催化剂。 该催化剂具有优异的储存稳定性和热稳定性。
    • 4. 发明授权
    • Solid catalyst component for .alpha.-olefin polymerization and process
for the producing the same
    • 用于α-烯烃聚合的固体催化剂组分及其制备方法
    • US4724225A
    • 1988-02-09
    • US935723
    • 1986-11-28
    • Hiroshi ShimizuToshihiro UwaiMasami Tachibana
    • Hiroshi ShimizuToshihiro UwaiMasami Tachibana
    • B01J31/38B01J37/00C08F4/60C08F4/64C08F4/642C08F10/00C08F10/06
    • C08F10/00Y10S526/901Y10S526/908Y10S526/909
    • A solid catalyst component which can produce .alpha.-olefin polymers having a high stereoregularity and a good powder fluidity, stably and with a good efficiency in gas phase polymerization, particularly in gas phase copolymerization, a catalyst for .alpha.-olefin polymerization using the above solid catalyst component and a process for producing the above catalyst component, are provided,which solid catalyst component is charcterized in that it contains titanium as an active ingredient and is in the form of hollow fine particles, andwhich process is characterized by adding a reaction product (I) of an organoaluminum compound (A) with an electron dnor (B.sub.1) to TiCl.sub.4 and reacting these under agitation in a baffle ratio of 0.35 or less with a power required for agitation of 2.50 KW/m.sup.3 or less at a temperature of 0.degree. to 70.degree. C. for a period of 1 to 10 hours and further reacting an electron donor (B.sub.2) and an electron acceptor (E) with the resulting solid product (II) to obtain a solid product (III) i.e. the solid catalyst component.
    • 一种固体催化剂组分,其可以生产具有高立构规整性和良好的粉末流动性的α-烯烃聚合物,并且在气相聚合中,特别是在气相共聚中具有良好的效率,使用上述固体催化剂的α-烯烃聚合催化剂 组分和制备上述催化剂组分的方法,该固体催化剂组分的特征在于其含有钛作为活性成分,并且为中空微粒形式,该方法的特征在于加入反应产物( I)具有电子dnor(B1)至TiCl 4的有机铝化合物(A),并在0.35℃或更小的挡板搅拌下将其与在0℃的温度下搅拌所需的功率为2.50KW / m 3或更小的反应 至70℃,持续1至10小时,并使电子给体(B2)和电子受体(E)与所得固体产物(II)反应,得到固体p (III),即固体催化剂组分。
    • 5. 发明授权
    • Catalysts for polymerization of olefins
    • 用于烯烃聚合的催化剂
    • US5084429A
    • 1992-01-28
    • US563613
    • 1990-08-07
    • Masami TachibanaToshihiro UwaiTetsuya MatsukawaTeruaki Hayashida
    • Masami TachibanaToshihiro UwaiTetsuya MatsukawaTeruaki Hayashida
    • C08F10/10C08F4/637C08F4/646C08F4/653C08F4/654C08F4/656C08F4/658C08F4/685C08F10/00
    • C08F10/00
    • A catalyst for use in polymerization of olefins which comprises a carrier mainly composed of a magnesium compound precipitated from a solution and a catalytic component supported on the carrier and selected from titanium halides, vanadyl halides and vanadium halides is described. The catalyst is obtained by a process which comprises: (A) mixing (a) at least one magnesium compound with (c) a saturated or unsaturated monohydric or polyhydric alcohol for reaction in dissolved state in the presence of (b) carbon dioxide in an inert hydrocarbon solvent to obtain component (A); (B) subjecting the component (A) to mixing and reaction with (d) a titanium and/or a vanadyl halide and/or a vanadium halide of the general formula, VX.sub.r (OR.sup.8).sub.4-r, and also with (e) at least one boron compound, Si compound and/or Siloxane compound thereby obtaining solid product (I); (C) reacting the solid product (I) with (f) a cyclic ether with or without R.sup.12 OH thereby causing dissolution and re-precipitation to obtain solid product (II); and (D) subjecting the solid product (II) to further reaction with (g) component (B) consisting of a titanium halide and/or a vanadyl halide and/or a vanadium halide, and/or a SiX.sub. s (OR.sup.9).sub.4-s, thereby obtaining solid product (III), followed either by further reaction with a mixture of the component (B) and (h) an electron donor or by reaction of (g) with the solid product (III) obtained by the reaction between the solid product (II) and (h) or (h) with (j) electron donor, thereby obtaining solid product (IV) for use as the catalytic component.
    • 8. 发明授权
    • Catalyst component for olefin polymerization
    • 用于烯烃聚合的催化剂组分
    • US5122490A
    • 1992-06-16
    • US738929
    • 1991-08-01
    • Toshihiro UwaiMasami TachibanaTeruaki Hayashida
    • Toshihiro UwaiMasami TachibanaTeruaki Hayashida
    • C08F4/658C08F4/60C08F4/64C08F10/00
    • C08F10/00
    • A catalyst component for olefin polymerization composed of a solid component (IV) and capable of affording a supported type catalyst composed of large particles and having a sharp particle size distribution is provided,which solid component (IV) is obtained bystep A of reacting an organic Mg compound of a specified formula with a 1-20C saturated or unsaturated mono- or polyhydric alcohol C in the presence of CO.sub.2 b;step B of reacting the resulting component A, with a Ti halide (IV) and/or a vanadyl halide and/or a V halide and/or a halogenated silane d and an organic B compound of a specified formula or a siloxane compound of a specified formula or a silane compound having Si-O-Si bond;Step C of reacting the resulting solid product (I) with a 1-20C saturated or unsaturated mono- or polyhydric alcohol f, an electron donor g and a cyclic ether h; andstep D of reacting the resulting solid product (II) with component B i comprising Ti halide and/or vanadyl halide and/or V halide and/or halogenated silane, followed by reacting the resulting solid product (III) with component B j and an electron donor k.
    • 提供了一种由固体成分(Ⅳ)构成并能够提供由大颗粒构成的具有尖锐的粒度分布的负载型催化剂的烯烃聚合用催化剂组分,该固体组分(Ⅳ)是通过步骤A 在CO 2 + E,crc / b /的存在下,具有1-20C饱和或不饱和单或多元醇+ E,crc / C /的特定式的有机Mg化合物; 使所得组分A与Ti卤化物(IV)和/或氧化钒和/或V卤化物和/或卤代硅烷+ E,crc / d /和具有规定式的有机B化合物反应的步骤B 或具有规定式的硅氧烷化合物或具有Si-O-Si键的硅烷化合物; 使得到的固体产物(I)与1-20C饱和或不饱和一价或多元醇+ E,crc / f /,电子给体+ E,crc / g /和环醚+ E,crc反应的步骤C /H/ ; 和步骤D使所得固体产物(II)与组分B + E,crc / i /包含Ti卤化物和/或氧化钒和/或V卤化物和/或卤化硅烷反应,然后使所得固体产物(III )与组分B + E,crc / j /和电子给体+ E,crc / k /。
    • 9. 发明授权
    • Process for producing .alpha.-olefin polymers
    • 制备α-烯烃聚合物的方法
    • US4363901A
    • 1982-12-14
    • US233778
    • 1981-02-12
    • Kazutsune KikutaMasami TachibanaAkihiro Sato
    • Kazutsune KikutaMasami TachibanaAkihiro Sato
    • C08F2/00C08F2/34C08F4/00C08F4/60C08F10/00C08F4/02
    • C08F10/00Y10S526/901Y10S526/902
    • A process for producing high-quality .alpha.-olefin polymers with a higher yield in a long lasting stabilized manner even in the case of gas phase polymerization is provided. In the production process of .alpha.-olefin polymers which comprises reacting a trivalent metal halide with a divalent metal compound to obtain a solid product (I); reacting this product with at least one electron donor (ED) and at least one electron acceptor (EA), once to 10 times, and at that time, using TiCl.sub.4 at least once as the (EA) to obtain a solid product (II); combining this product with an organoaluminum compound (OAl) and an (ED) (these three being referred to as catalyst components), the improvement which comprises subjecting a part or the whole of the catalyst components to polymerization treatment with a small amount of an .alpha.-olefin, at least in the coexistence of the solid product (II) and (OAl), in the combination of the catalyst components to obtain a preactivated catalyst, and subjecting .alpha.-olefin(s) to gas phase polymerization or bulk or slurry polymerization followed by gas phase polymerization, using the catalyst.
    • 提供了即使在气相聚合的情况下也以长时间稳定的方式生产具有较高产率的高品质α-烯烃聚合物的方法。 在α-烯烃聚合物的制造方法中,包括使三价金属卤化物与二价金属化合物反应得到固体产物(I); 使该产物与至少一种电子给体(ED)和至少一种电子受体(EA)反应一次至10次,此时使用TiCl 4至少一次作为(EA)获得固体产物(II) ; 将该产物与有机铝化合物(OAl)和(ED)(这三种被称为催化剂组分)组合,其改进包括使部分或全部催化剂组分用少量的α进行聚合处理 至少在固体产物(II)和(OAl)共存的情况下,在催化剂组分的组合中获得预活化的催化剂,并使α-烯烃进行气相聚合或本体或淤浆聚合 然后使用催化剂进行气相聚合。
    • 10. 发明授权
    • Process for producing .alpha.-olefin polymers
    • 制备α-烯烃聚合物的方法
    • US4304891A
    • 1981-12-08
    • US144555
    • 1980-04-28
    • Akihiro SatoMasami TachibanaKazutsune KikutaYoshiharu Higuchi
    • Akihiro SatoMasami TachibanaKazutsune KikutaYoshiharu Higuchi
    • C08F2/00C08F2/34C08F4/00C08F4/10C08F4/12C08F4/16C08F4/60C08F4/64C08F10/00C08F4/02
    • C08F10/00Y10S526/901Y10S526/902Y10S526/904
    • A process for producing .alpha.-olefins is provided which comprises:milling (A) a trivalent metal halide together with (B) a divalent metal compound, in a specified ratio of (A) to (B), and reacting them to obtain a solid product (I);reacting with this product (I), (C) an electron donor and (D) an electron acceptor, (C) and (D) being respectively reacted once or more up to ten times, and TiCl.sub.4 being employed as the electron acceptor at least once, to obtain a solid product (II);combining with this product (II), (E) a trialkylaluminum and (G) a reaction product of an electron donor with an electron acceptor, and in this combination, subjecting a part or the whole of the catalyst components (product (II), (E) and (G)) to polymerization treatment by reacting (F) an .alpha.-olefin at least in the presence of the product (II) and trialkylaluminum, to obtain a preliminarily activated catalyst; andpolymerizing an .alpha.-olefin in the presence of this catalyst.The above catalyst is suitable particularly for gas phase polymerization or suspension or bulk polymerization followed by gas phase polymerization, and affords a highly crystalline .alpha.-olefin polymer having a good particle form, with a high yield.
    • 提供了制备α-烯烃的方法,其包括:(A)三价金属卤化物与(B)二价金属化合物以(A)至(B)的规定比例研磨,并使其反应获得固体 产品(I); 与该产物(I),(C)电子给体和(D)电子受体反应,(C)和(D)分别反应一次或多达十次,并且至少使用TiCl 4作为电子受体 一次,得到固体产物(II); 与该产物(II),(E)三烷基铝和(G)电子给体与电子受体的反应产物(II),(E),并且在这种组合中,将一部分或全部催化剂组分(产物(II) (E)和(G))通过至少在产物(II)和三烷基铝的存在下使(F)α-烯烃反应进行聚合处理,得到预活化的催化剂; 并在该催化剂存在下聚合α-烯烃。 上述催化剂特别适用于气相聚合或悬浮或本体聚合,然后进行气相聚合,并以高产率提供具有良好颗粒形式的高结晶性α-烯烃聚合物。