公开(公告)号：US08288488B2

公开(公告)日：2012-10-16

申请号：US13094268

申请日：2011-04-26

Applicant: Yasuki Fujiwara ,  Wataru Hirahata ,  Hirofumi Hamaki

Inventor： Yasuki Fujiwara ,  Wataru Hirahata ,  Hirofumi Hamaki

IPC: C08F4/42 ,  C08F4/60

CPC classification number: C08F10/00 ,  C08F110/06 ,  C08F4/6548 ,  C08F4/651 ,  C08F2500/17 ,  C08F2500/15

Abstract: The present invention aims at providing a process for producing a solid catalyst for olefin polymerization, the solid catalyst component being capable of providing a polymer having high stereoregularity when an α-olefin is polymerized; a process for producing a solid catalyst component, which is used for producing the solid catalyst; and a process for producing an olefin polymer using the solid catalyst. This object can be achieved by a process for producing a solid catalyst component (A), the process including a step of bringing a titanium compound (a), a magnesium compound (b) and an internal electron donor represented by Formula (I) into contact with each other: where R1 is a hydrocarbyl group having 1 to 20 carbon atoms; R2, R3, R4, and R5 are each independently selected from a hydrogen atom, a halogen atom and a hydrocarbyl group having 1 to 20 carbon atoms, and at least one selected from R2, R3, R4, and R5 is a hydrocarbyl group having 1 to 20 carbon atoms; and R6 is a halogen atom.

Abstract translation: 本发明的目的在于提供一种用于烯烃聚合的固体催化剂的制备方法，该固体催化剂组分能够提供当α-烯烃聚合时具有高立构规整性的聚合物; 用于制备固体催化剂的固体催化剂组分的制备方法; 以及使用该固体催化剂制造烯烃聚合物的方法。 该目的可以通过制备固体催化剂组分（A）的方法来实现，该方法包括将由式（I）表示的钛化合物（a），镁化合物（b）和内给电子体引入到 彼此接触：其中R1是具有1-20个碳原子的烃基; R2，R3，R4和R5各自独立地选自氢原子，卤素原子和具有1至20个碳原子的烃基，并且选自R2，R3，R4和R5中的至少一个是具有 1至20个碳原子; R6为卤素原子。

公开(公告)号：US20110275765A1

公开(公告)日：2011-11-10

申请号：US13162998

申请日：2011-06-17

Applicant: Yasuki FUJIWARA ,  Makoto SATOH ,  Shinya NAKAHARA ,  Shin-ichi KUMAMOTO

Inventor： Yasuki FUJIWARA ,  Makoto SATOH ,  Shinya NAKAHARA ,  Shin-ichi KUMAMOTO

IPC: C08L23/16 ,  C08F4/649

CPC classification number: C08F210/16 ,  C08L23/0815 ,  C08L23/10 ,  C08L23/142 ,  C08L2666/06 ,  C08F210/06 ,  C08F2500/17 ,  C08F2500/20 ,  C08F2500/12 ,  C08F2500/04 ,  C08F2500/21

Abstract: There are provided an ethylene-propylene copolymer having the following structural characteristics, and a polypropylene resin composition comprising the above copolymer and polypropylene having a melting temperature of 160° C. or higher: (1) its propylene content is 20 to 60% by mol; (2) its product of a monomer reactivity ratio is less than 2.5; (3) its intrinsic viscosity is more than 1.0 dl/g; (4) its molecular weight distribution is more than 3; (5) its glass transition temperature is lower than −40° C.; (6) its heat of crystallization is less than 5.0 J/g; (7) in a temperature rising elution fractionation method, its elution amount is 60% by weight or more in a temperature range of lower than 10° C., its elution amount is 3% by weight or more in a temperature range of 10° C. to lower than 55° C., and its elution amount is 5% by weight or less in a temperature range of 83° C. or higher, provided that the total elution amount is 100% by weight; and (8) an intensity ratio of a racemic peak to a meso peak in an ethylene-propylene binding moiety in a 13C-NMR spectrum is 0.01 to 0.7.

Abstract translation: 提供具有以下结构特征的乙烯 - 丙烯共聚物，以及包含上述共聚物和熔融温度为160℃以上的聚丙烯的聚丙烯树脂组合物：（1）丙烯含量为20〜60摩尔％ ; （2）其单体反应率的乘积小于2.5; （3）其特性粘度大于1.0dl / g; （4）其分子量分布大于3; （5）其玻璃化转变温度低于-40℃; （6）其结晶热小于5.0J / g; （7）在升温洗脱分馏方法中，在低于10℃的温度范围内的洗脱量为60重量％以上，在10℃的温度范围内的洗脱量为3重量％以上 在83℃以上的温度范围内，其洗脱量为5重量％以下，前提条件是总洗脱量为100重量％ 和（8）13 C-NMR光谱中的乙烯 - 丙烯结合​​部分中的外消旋峰与内消旋峰的强度比为0.01〜0.7。

公开(公告)号：US08039552B2

公开(公告)日：2011-10-18

申请号：US12493296

申请日：2009-06-29

Applicant: Yasuki Fujiwara

Inventor： Yasuki Fujiwara

IPC: C08L53/00 ,  C08F4/00 ,  C08F210/00 ,  C08F110/06

CPC classification number: C08F297/08 ,  C08F210/06 ,  C08F297/083 ,  C08L53/00 ,  C08L2666/02 ,  C08F210/16 ,  C08F2500/17

Abstract: A production process of a propylene block copolymer, comprising the step (I) of polymerizing propylene alone or a combination of propylene with an olefin other than propylene, in the presence of a defined polymerization catalyst, to form a polymer component (1), and the step (II) of copolymerizing propylene with an olefin other than propylene in the presence of the polymer component (1), to form a polymer component (2), wherein a combination of a transition metal compound such as Zr(OR1)4 and Hf(OR1)4 (R1 being a hydrocarbon group) with an ether group-containing linear hydrocarbon compound and/or a Lewis base compound is added to the above polymerization system between the ending point of the step (I) and the starting point of the step (II), or during the step (II).

Abstract translation: 丙烯嵌段共聚物的制备方法包括在限定的聚合催化剂的存在下单独聚合丙烯或丙烯与丙烯以外的烯烃的组合的步骤（I）以形成聚合物组分（1），和 在聚合物组分（1）的存在下使丙烯与丙烯以外的烯烃共聚以形成聚合物组分（2）的步骤（II），其中过渡金属化合物如Zr（OR 1）4和 在步骤（I）的终点和起始点之间的上述聚合体系中加入与含醚基的直链烃化合物和/或路易斯碱化合物的Hf（OR 1）4（R 1为烃基） 步骤（II），或在步骤（II）期间。

公开(公告)号：US20100168349A1

公开(公告)日：2010-07-01

申请号：US12630894

申请日：2009-12-04

Applicant: Yasuki FUJIWARA

Inventor： Yasuki FUJIWARA

IPC: C08F4/76 ,  C08F10/00

CPC classification number: C08F10/06 ,  C08F110/06 ,  C08F4/6465 ,  C08F4/6494 ,  C08F4/6492 ,  C08F4/6565 ,  C08F2500/15 ,  C08F2500/17

Abstract: A production process of an α-olefin polymerization catalyst, comprising the steps of (1) reducing a titanium compound represented by a defined formula with an organomagnesium compound in the presence of an Si—O bond-containing silicon compound, (2) contacting the resultant solid catalyst component precursor, a halogenating compound and an internal electron donor with one another, and (3) contacting the resultant solid catalyst component, an organoaluminum compound and a Si-containing external electron donor represented by a defined formula with one another; and a production process of an olefin polymer using the above catalyst.

Abstract translation: 一种α-烯烃聚合催化剂的制备方法，包括以下步骤：（1）在含Si-O键的硅化合物的存在下，用有机镁化合物还原由定义的式表示的钛化合物，（2）使 生成的固体催化剂组分前体，卤化化合物和内部电子给体，和（3）使所得固体催化剂组分，有机铝化合物和由所定义的式表示的含Si的外部电子给体彼此接触; 以及使用上述催化剂的烯烃聚合物的制造方法。

公开(公告)号：US20100004395A1

公开(公告)日：2010-01-07

申请号：US12493296

申请日：2009-06-29

Applicant: Yasuki FUJIWARA

Inventor： Yasuki FUJIWARA

IPC: C08L53/00

CPC classification number: C08F297/08 ,  C08F210/06 ,  C08F297/083 ,  C08L53/00 ,  C08L2666/02 ,  C08F210/16 ,  C08F2500/17

Abstract: A production process of a propylene block copolymer, comprising the step (I) of polymerizing propylene alone or a combination of propylene with an olefin other than propylene, in the presence of a defined polymerization catalyst, to form a polymer component (1), and the step (II) of copolymerizing propylene with an olefin other than propylene in the presence of the polymer component (1), to form a polymer component (2), wherein a combination of a transition metal compound such as Zr(OR1)4 and Hf(OR1)4 (R1 being a hydrocarbon group) with an ether group-containing linear hydrocarbon compound and/or a Lewis base compound is added to the above polymerization system between the ending point of the step (I) and the starting point of the step (II), or during the step (II).

Abstract translation: 丙烯嵌段共聚物的制备方法包括在限定的聚合催化剂的存在下单独聚合丙烯或丙烯与丙烯以外的烯烃的组合的步骤（I）以形成聚合物组分（1），和 在聚合物组分（1）的存在下使丙烯与丙烯以外的烯烃共聚以形成聚合物组分（2）的步骤（II），其中过渡金属化合物如Zr（OR 1）4和 在步骤（I）的终点和起始点之间的上述聚合体系中加入与含醚基的直链烃化合物和/或路易斯碱化合物的Hf（OR 1）4（R 1为烃基） 步骤（II），或在步骤（II）期间。

公开(公告)号：US20090326158A1

公开(公告)日：2009-12-31

申请号：US12514479

申请日：2007-12-14

Applicant: Yasuki Fujiwara

Inventor： Yasuki Fujiwara

IPC: C08F10/06 ,  C08L53/00

CPC classification number: C08F297/083 ,  C08F210/06 ,  C08F210/16 ,  C08F297/08 ,  C08F2410/01 ,  C08L23/08 ,  C08L23/10 ,  C08L53/00 ,  C08F2/001 ,  C08F4/65927 ,  C08L2666/06 ,  C08F2500/17 ,  C08F2500/15 ,  C08F2500/12 ,  C08F2500/11

Abstract: A propylene block copolymer satisfying the following requirements, which is obtained by producing in the step 1 a propylene polymer component (1), producing in the step 2 a propylene copolymer component (2) in the presence of the component (1), and producing in the step 3 an ethylene copolymer component (3) in the presence of the components (1) and (2): the component (1) has a melting temperature of 155° C. or higher; the component (2) contains 40 to 50% by mol of ethylene, and has an intrinsic viscosity of 2.0 to 8.0 dl/g; the component (3) contains 45 to 70% by mol of ethylene, and has an intrinsic viscosity of 3.0 to 8.0 dl/g, provided that the ethylene content is larger than the ethylene content in the propylene polymer component (2); a ratio by weight of the component (2) to the component (3) is 1/10 to 1/1; the propylene block copolymer has a glass transition temperature of −55.0° C. or lower; and dispersed particles contained in an injection molded article of the block copolymer have a volume-average particle diameter of 1.0 μm or less, provided that the above particles have a round shape in their cross-section.

Abstract translation: 一种满足以下要求的丙烯嵌段共聚物，其通过在步骤1中制备丙烯聚合物组分（1），在步骤2中在组分（1）的存在下制备丙烯共聚物组分（2），并产生 在步骤3中，在组分（1）和（2）存在下，乙烯共聚物组分（3）：组分（1）的熔融温度为155℃或更高; 成分（2）含有40〜50摩尔％的乙烯，特性粘度为2.0〜8.0dl / g， 乙烯的含量比丙烯聚合物成分（2）中的乙烯含量大，成分（3）含有45〜70摩尔％的乙烯，特性粘度为3.0〜8.0分升/克。 组分（2）与组分（3）的重量比为1/10至1/1; 丙烯嵌段共聚物的玻璃化转变温度为-55.0℃以下; 并且嵌段共聚物的注塑成型体中所含的分散粒子的体积平均粒径为1.0μm以下，只要上述粒子的截面为圆形即可。

公开(公告)号：US07135532B2

公开(公告)日：2006-11-14

申请号：US10958272

申请日：2004-10-06

Applicant: Yasuki Fujiwara ,  Makoto Satoh

Inventor： Yasuki Fujiwara ,  Makoto Satoh

IPC: C08F4/44

CPC classification number: C08F10/00 ,  C08F110/06 ,  C08F4/651 ,  C08F4/6565 ,  C08F2500/17 ,  C08F2500/18

Abstract: There are disclosed a process for producing a solid catalyst component and a catalyst for α-olefin polymerization, and a process for producing an α-olefin polymer, wherein the process for producing a solid catalyst component comprises the steps of: (1) reducing a specific titanium compound with an organomagnesium compound in the presence of an organosilicon compound having an Si—O bond (and an ester compound), thereby obtaining a solid product, and (2) contacting the solid product with a halogeno compound of the 14 group element, at least one member selected from the group consisting of an electron donor compound and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining the solid catalyst component.

Abstract translation: 公开了一种制备固体催化剂组分和用于α-烯烃聚合的催化剂的方法，以及制备α-烯烃聚合物的方法，其中固体催化剂组分的制备方法包括以下步骤：（1）将 在具有Si-O键的有机硅化合物（和酯化合物）存在下，使用具有有机镁化合物的钛化合物，得到固体产物，和（2）使固体产物与14族元素的卤代化合物接触 ，选自电子给体化合物和有机酰卤的至少一种，和具有Ti-卤键的化合物，从而获得固体催化剂组分。

公开(公告)号：US06841503B2

公开(公告)日：2005-01-11

申请号：US09773750

申请日：2001-02-02

Applicant: Yasuki Fujiwara ,  Makoto Satoh

Inventor： Yasuki Fujiwara ,  Makoto Satoh

IPC: C08F4/649 ,  C08F4/76 ,  C08F10/00 ,  C08F110/06 ,  B01J31/00 ,  B01J31/16

CPC classification number: C08F10/00 ,  C08F110/06 ,  C08F4/651 ,  C08F4/6565 ,  C08F2500/17 ,  C08F2500/18

Abstract: There are disclosed a process for producing a solid catalyst component and a catalyst for α-olefin polymerization, and a process for producing an α-olefin polymer, wherein the process for producing a solid catalyst component comprises the steps of: (1) reducing a specific titanium compound with an organomagnesium compound in the presence of an organosilicon compound having an Si—O bond (and an ester compound), thereby obtaining a solid product, and (2) contacting the solid product with a halogeno compound of the 14 group element, at least one member selected from the group consisting of an electron donor compound and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining the solid catalyst component.

Abstract translation: 公开了一种制备固体催化剂组分和用于α-烯烃聚合的催化剂的方法，以及制备α-烯烃聚合物的方法，其中固体催化剂组分的制备方法包括以下步骤：（1）将 在具有Si-O键的有机硅化合物（和酯化合物）存在下，使用具有有机镁化合物的钛化合物，得到固体产物，和（2）使固体产物与14族元素的卤代化合物接触 ，选自电子给体化合物和有机酰卤的至少一种，和具有Ti-卤键的化合物，从而获得固体催化剂组分。

公开(公告)号：US08138284B2

公开(公告)日：2012-03-20

申请号：US12642153

申请日：2009-12-18

Applicant: Yasuki Fujiwara

Inventor： Yasuki Fujiwara

IPC: C08F4/00 ,  C08F4/06 ,  C08F4/44 ,  C08F210/00 ,  C08F110/06

CPC classification number: C08F10/06 ,  C08F210/06 ,  C08F297/083 ,  C08F4/6494 ,  C08F4/6565 ,  C08F4/6465 ,  C08F4/6492 ,  C08F210/16 ,  C08F2500/17 ,  C08F2500/15

Abstract: A production process of a propylene block copolymer, comprising the steps of (I) contacting a solid catalyst component containing titanium atoms, magnesium atoms and halogen atoms with an organoaluminum compound and an external electron donor represented by the defined formula, thereby forming a polymerization catalyst, (II) polymerizing propylene in the presence of the polymerization catalyst, thereby forming a polymer component (1) having an intrinsic viscosity, [η]1, and (III) copolymerizing propylene with an olefin other than propylene in the presence of the polymer component (1), thereby forming a polymer component (2) having an intrinsic viscosity, [η]2, which is three times or more [η]1.

Abstract translation: 一种丙烯嵌段共聚物的制造方法，包括以下步骤：（I）使含有钛原子，镁原子和卤素原子的固体催化剂组分与有机铝化合物和由定义的式表示的外部电子给体接触，从而形成聚合催化剂 ，（II）在聚合催化剂存在下聚合丙烯，从而形成具有特性粘度[η]的聚合物组分（1），和（III）在丙烯存在下使丙烯与丙烯以外的烯烃共聚 聚合物组分（1），从而形成具有特性粘度[[eegr]] 2的聚合物组分（2），其为[3]以上3倍以上。

公开(公告)号：US08119738B2

公开(公告)日：2012-02-21

申请号：US12515135

申请日：2007-12-14

Applicant: Yasuki Fujiwara ,  Shuichi Kimata ,  Hideki Oshima

Inventor： Yasuki Fujiwara ,  Shuichi Kimata ,  Hideki Oshima

IPC: C08F8/00 ,  C08L23/00 ,  C08L23/04 ,  C08L23/10

CPC classification number: C08L23/12 ,  C08L23/0815 ,  C08L2666/06

Abstract: There are provided a polypropylene resin composition and a molded article thereof, the composition comprising: 60 to 85% by weight of a propylene homopolymer; and 15 to 40% by weight of an ethylene-α-olefin random copolymer containing 45 to 70 parts by mol of ethylene units, and 30 to 55 parts by mol of α-olefin units, and satisfying the following requirements (1) to (5), (1) the propylene homopolymer has a melting temperature of 163 to 170° C.; (2) the propylene homopolymer contains 0.01% or less of regio defects resulted from a 2,1-insertion and a 1,3-insertion in all propylene units; (3) the polypropylene resin composition has a ratio B/A of 0.9 or more, provided that A (% by weight) is an amount of the ethylene-α-olefin random copolymer contained in the polypropylene resin composition, and B (% by weight) is an amount of soluble parts in xylene at a room temperature contained in the polypropylene resin composition; (4) the ethylene-α-olefin random copolymer has a molecular weight distribution of 2.0 to 4.0; and (5) the ethylene-α-olefin random copolymer contained in the polypropylene resin composition has a shape of a particle, whose volume-average particle diameter is 1.0 μm or less, measured by observing a cross-section of a 0.5 mm-thick sheet with a transmission electron microscopy, the sheet being obtained by hot press-molding the above polypropylene resin composition at 190° C. for 3 minutes under a pressure of 35 kgf/cm2, provided that the cross-section of the above particle has a round shape.

Abstract translation: 提供一种聚丙烯树脂组合物及其模制品，该组合物包含：60-85重量％的丙烯均聚物; 和15〜40重量％的含有45〜70摩尔的乙烯单元的乙烯-α-烯烃无规共聚物和30〜55摩尔的α-烯烃单元，满足下述（1）〜（ 5），（1）丙烯均聚物的熔融温度为163〜170℃。 （2）丙烯均聚物含有0.01％以下的所有丙烯单元中的2,1-插入和1,3-插入引起的区域缺陷; （3）聚丙烯树脂组合物的B / A比为0.9以上，A（重量％）为聚丙烯树脂组合物中所含的乙烯-α-烯烃无规共聚物的量，B（％ 重量）是包含在聚丙烯树脂组合物中的在室温下的二甲苯中的可溶部分的量; （4）乙烯-α-烯烃无规共聚物的分子量分布为2.0〜4.0; 和（5）包含在聚丙烯树脂组合物中的乙烯-α-烯烃无规共聚物的体积平均粒径为1.0μm以下的颗粒的形状，通过观察0.5mm厚的横截面 通过透射电子显微镜观察，片材通过在35kgf / cm 2的压力下在190℃下热压成型上述聚丙烯树脂组合物3分钟而获得，条件是上述颗粒的横截面为 圆形。