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1. 发明授权

US08133835B2 Molecular weight controllable, high 1,4-trans polybutadiene catalyst system 有权
标题翻译：分子量可控，高的1,4-反式聚丁二烯催化剂体系
公开(公告)号：US08133835B2
公开(公告)日：2012-03-13
申请号：US12686104
申请日：2010-01-12
申请人： Hwieon Park , Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee
发明人： Hwieon Park , Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee
IPC分类号： B01J31/04 , C08F4/70 , C08F136/06
CPC分类号： C08L9/06 , C08F136/06 , C08K5/057 , C08K5/098 , C08K5/527 , C08L7/00 , C08L9/00 , C08L21/00 , C08L2205/02 , C08L2205/035 , C08F4/7096 , C08L2666/02 , C08L2666/08
摘要： Provided are a molecular weight controllable, high 1,4-trans polybutadiene catalyst system, and more particularly, a four-component catalyst for preparing 1,4-trans polybutadiene with high yield, the catalyst comprising a cobalt compound, an organoaluminum compound, a phenol-based compound, and a phosphorus-based compound used to prepare 1,4-trans polybutadiene by polymerizing butadiene or a butadiene derivative, and capable of controlling the molecular weight of 1,4-trans polybutadiene by regulating the amount of the phosphorus-based compound. In particular, 1,4-trans polybutadiene may be efficiently applied to tires, belts, or the like since it has excellent tensile strength, tear strength, and cut & chip properties with increasing processability.
摘要翻译：提供了分子量可控的高的1,4-反式聚丁二烯催化剂体系，更具体地说，提供了一种用于以高产率制备1,4-反式聚丁二烯的四组分催化剂，该催化剂包括钴化合物，有机铝化合物，苯酚类化合物和用于通过聚合丁二烯或丁二烯衍生物制备1,4-反式聚丁二烯的磷系化合物，并且能够通过调节含磷的化合物的量来控制1,4-反式聚丁二烯的分子量，基化合物。特别地，1,4-反式聚丁二烯可以有效地施加到轮胎，皮带等上，因为它具有优异的拉伸强度，撕裂强度以及切削和切削性能以及加工性能的提高。

2. 发明授权

US06506865B2 Monomeric neodymium carboxylate and its use in polymerization of conjugated diene 失效
公开(公告)号：US06506865B2
公开(公告)日：2003-01-14
申请号：US10146312
申请日：2002-05-15
申请人： Gwang Hoon Kwag , Seung Hwon Lee , Young Chan Jang , A Ju Kim
发明人： Gwang Hoon Kwag , Seung Hwon Lee , Young Chan Jang , A Ju Kim
IPC分类号： C08F452
CPC分类号： C08F236/08 , C07F5/003 , C08F236/06 , C08F4/545
摘要： The invention is related to a novel compound represented by NdHA4 wherein A is a carboxylate, and to a diene polymerization catalyst using the novel compound. NdHA4 has monomeric structure and does not contain water, bases and salts. NdHA4 is mixed with a halogen compound and an organic metal compound to prepare a catalyst system. The catalyst system in the polymerization of 1,3-butadiene (BD) or isoprene produces high cis polydiene with a high activity (100 g BD/4.0×10−5 mole Nd) and without gel formation. The polydiene thus obtained is useful for tires and golf balls and as a polystyrene modifier.

3. 发明授权

US08552120B2 Grafted and functionalized high 1,4-trans polybutadiene with aromatic organosulfur compound 有权
标题翻译：接枝和官能化高的1,4-反式聚丁二烯与芳族有机硫化合物
公开(公告)号：US08552120B2
公开(公告)日：2013-10-08
申请号：US12560784
申请日：2009-09-16
申请人： Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee , Hwieon Park , Hyung Kyu Choi
发明人： Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee , Hwieon Park , Hyung Kyu Choi
IPC分类号： C08C19/20 , C08C19/28
CPC分类号： C08C19/20 , C08L7/00 , C08L9/06 , C08L15/00 , C08L2205/03 , C08L2666/02
摘要： The present invention relates to a process of preparing 1,4-trans polybutadiene grafted with an aromatic organosulfur compound, the process comprising (a) preparing 1,4-trans polybutadiene by polymerizing 1,3-butadiene or butadiene derivatives in a nonpolar solvent in the presence of a particular catalyst, and (b) preparing the 1,4-trans polybutadiene grafted with an aromatic organosulfur compound by reacting the trans polybutadiene with an aromatic organosulfur compound. The organosulfur molecule in the molecular chain minimizes ultra high molecular weight fraction and narrows the molecular weight distribution, thereby enabling this polymer to show improved processability and tensile properties.
摘要翻译：本发明涉及一种制备用芳族有机硫化合物接枝的1,4-反式聚丁二烯的方法，该方法包括（a）通过在非极性溶剂中聚合1,3-丁二烯或丁二烯衍生物制备1,4-反式聚丁二烯特定催化剂的存在，和（b）通过使反式聚丁二烯与芳族有机硫化合物反应制备与芳族有机硫化合物接枝的1,4-反式聚丁二烯。分子链中的有机硫分子使超高分子量分数最小化并使分子量分布变窄，从而使该聚合物显示改进的加工性能和拉伸性能。

4. 发明申请

US20100081770A1 GRAFTED AND FUNCTIONALIZED HIGH 1,4-TRANS POLYBUTADIENE WITH AROMATIC ORGANOSULFUR COMPOUND 有权
标题翻译：具有芳香族有机化合物的接枝和功能化的高度1,4-转移聚丁二烯
公开(公告)号：US20100081770A1
公开(公告)日：2010-04-01
申请号：US12560784
申请日：2009-09-16
申请人： Gwang Hoon KWAG , Hoochae Kim , Seung Hwon Lee , Hwieon Park , Hyung Kyu Choi
发明人： Gwang Hoon KWAG , Hoochae Kim , Seung Hwon Lee , Hwieon Park , Hyung Kyu Choi
IPC分类号： C08F28/02 , B01J31/14
CPC分类号： C08C19/20 , C08L7/00 , C08L9/06 , C08L15/00 , C08L2205/03 , C08L2666/02
摘要： The present invention relates to a process of preparing 1,4-trans polybutadiene grafted with an aromatic organosulfur compound, the process comprising (a) preparing 1,4-trans polybutadiene by polymerizing 1,3-butadiene or butadiene derivatives in a nonpolar solvent in the presence of a particular catalyst, and (b) preparing the 1,4-trans polybutadiene grafted with an aromatic organosulfur compound by reacting the trans polybutadiene with an aromatic organosulfur compound. The organosulfur molecule in the molecular chain minimizes ultra high molecular weight fraction and narrows the molecular weight distribution, thereby enabling this polymer to show improved processability and tensile properties.
摘要翻译：本发明涉及一种制备用芳族有机硫化合物接枝的1,4-反式聚丁二烯的方法，该方法包括（a）通过在非极性溶剂中聚合1,3-丁二烯或丁二烯衍生物制备1,4-反式聚丁二烯特定催化剂的存在，和（b）通过使反式聚丁二烯与芳族有机硫化合物反应制备与芳族有机硫化合物接枝的1,4-反式聚丁二烯。分子链中的有机硫分子使超高分子量分数最小化并使分子量分布变窄，从而使该聚合物显示改进的加工性能和拉伸性能。

5. 发明授权

US06482930B1 Monomeric neodymium carboxylate and its use in polymerization of conjugated diene 失效
标题翻译：单体钕羧酸盐及其在共轭二烯聚合中的应用
公开(公告)号：US06482930B1
公开(公告)日：2002-11-19
申请号：US09690385
申请日：2000-10-17
申请人： Gwang Hoon Kwag , Seung Hwon Lee , Young Chan Jang , A Ju Kim
发明人： Gwang Hoon Kwag , Seung Hwon Lee , Young Chan Jang , A Ju Kim
IPC分类号： C07F500
CPC分类号： C08F236/08 , C07F5/003 , C08F236/06 , C08F4/545
摘要： The invention is related to a novel compound represented by NdHA4 wherein A is a carboxylate, and to a diene polymerization catalyst using the novel compound. NdHA4 has monomeric structure and does not contain water, bases and salts. NdHA4 is mixed with a halogen compound and an organic metal compound to prepare a catalyst system. The catalyst system in the polymerization of 1,3-butadiene (BD) or isoprene produces high cis polydiene with a high activity (100 g BD/4.0×10−5 mole Nd) and without gel formation. The polydiene thus obtained is useful for tires and golf balls and as a polystyrene modifier.
摘要翻译：本发明涉及一种由NdHA4表示的新型化合物，其中A为羧酸酯，并涉及使用该新化合物的二烯聚合催化剂。 NdHA4具有单体结构，不含水，碱和盐。将NdHA4与卤素化合物和有机金属化合物混合以制备催化剂体系。 1,3-丁二烯（BD）或异戊二烯聚合中的催化剂体系产生高活性的高顺式聚二烯（100g BD / 4.0×10-5摩尔Nd），不形成凝胶。如此获得的聚二烯可用于轮胎和高尔夫球以及作为聚苯乙烯改性剂。

6. 发明授权

US6013746A Process for controlling the molecular weight distribution of high 1,4-cis polybutadiene 失效
标题翻译：控制高1,4-顺式聚丁二烯分子量分布的方法
公开(公告)号：US6013746A
公开(公告)日：2000-01-11
申请号：US93646
申请日：1998-06-09
申请人： Young-Chan Jang , Gwang-Hoon Kwag , Dong-Il Yoon , A-Ju Kim , Kyung-Nam Lim
发明人： Young-Chan Jang , Gwang-Hoon Kwag , Dong-Il Yoon , A-Ju Kim , Kyung-Nam Lim
IPC分类号： C08F36/06 , C08F4/609 , C08F136/06 , C08F236/06 , C08F4/80
CPC分类号： C08F136/06
摘要： This invention relates to a process for controlling the molecular weight distribution of high 1,4-cis polybutadiene and more particularly, to a process of easily controlling the molecular weight distribution of polybutadiene which is concerned directly with the physical properties such as processability, in such a manner that preparation of high 1,4-cis polybutadiene is made available via polymerization of 1,3-butadiene in the presence of Ziegler-Natta catalyst, adding carboxylic acid represented by following formula I for the controlling of the molecular weight distribution of polybutadiene based on the contents of carboxylic acid, may be easily controlled, without any alternation in the 1,4-cis contents. ##STR1## Wherein R is selected from the group consisting of alkyl, cycloalkyl and arylalkyl groups substituted or unsubstituted with at least one or more halogen atoms, or alkyl, cycloalkyl and arylalkyl groups with at least one or more double bonds containing from 5 to 20 carbon atoms.
摘要翻译：本发明涉及一种控制高1,4-顺式聚丁二烯的分子量分布的方法，更具体地说，涉及容易控制聚丁二烯的分子量分布的方法，其直接关系到诸如加工性的物理性质通过在齐格勒 - 纳塔催化剂存在下，通过1,3-丁二烯的聚合可得到制备高1,4-顺式聚丁二烯的方式，加入由下式I表示的羧酸以控制聚丁二烯的分子量分布基于羧酸的含量，可以容易地控制，而在1,4-顺式含量中没有任何变化。其中R选自被至少一个或多个卤素原子取代或未取代的烷基，环烷基和芳基烷基，或具有至少一个或多个含有5至20个碳原子的双键的烷基，环烷基和芳烷基。

7. 发明申请

US20100261847A1 MOLECULAR WEIGHT CONTROLLABLE, HIGH 1,4-TRANS POLYBUTADIENE CATALYST SYSTEM 有权
标题翻译：分子量控制，高1,4转聚丁二烯催化剂体系
公开(公告)号：US20100261847A1
公开(公告)日：2010-10-14
申请号：US12686104
申请日：2010-01-12
申请人： Hwieon Park , Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee
发明人： Hwieon Park , Gwang Hoon Kwag , Hoochae Kim , Seung Hwon Lee
IPC分类号： C08L9/00 , C08F4/52
CPC分类号： C08L9/06 , C08F136/06 , C08K5/057 , C08K5/098 , C08K5/527 , C08L7/00 , C08L9/00 , C08L21/00 , C08L2205/02 , C08L2205/035 , C08F4/7096 , C08L2666/02 , C08L2666/08
摘要： Provided are a molecular weight controllable, high 1,4-trans polybutadiene catalyst system, and more particularly, a four-component catalyst for preparing 1,4-trans polybutadiene with high yield, the catalyst comprising a cobalt compound, an organoaluminum compound, a phenol-based compound, and a phosphorus-based compound used to prepare 1,4-trans polybutadiene by polymerizing butadiene or a butadiene derivative, and capable of controlling the molecular weight of 1,4-trans polybutadiene by regulating the amount of the phosphorus-based compound.In particular, 1,4-trans polybutadiene may be efficiently applied to tires, belts, or the like since it has excellent tensile strength, tear strength, and cut & chip properties with increasing processability.
摘要翻译：提供了分子量可控的高的1,4-反式聚丁二烯催化剂体系，更具体地说，提供了一种用于以高产率制备1,4-反式聚丁二烯的四组分催化剂，该催化剂包括钴化合物，有机铝化合物，苯酚类化合物和用于通过聚合丁二烯或丁二烯衍生物制备1,4-反式聚丁二烯的磷系化合物，并且能够通过调节含磷的化合物的量来控制1,4-反式聚丁二烯的分子量，基化合物。特别地，1,4-反式聚丁二烯可以有效地施加到轮胎，皮带等上，因为它具有优异的拉伸强度，撕裂强度以及切削和切削性能以及加工性能的提高。

8. 发明申请

US20090156751A1 Aromatic Organosulfur Functionalized 1,4-cis Polybutadiene 有权
标题翻译：芳香族有机硫官能化1,4-顺式聚丁二烯
公开(公告)号：US20090156751A1
公开(公告)日：2009-06-18
申请号：US12254505
申请日：2008-10-20
申请人： Gwang Hoon Kwag , Pil Sung Kim , Seung Hwon Lee , Hyung Kyu Choi , Hyun Jin Kim
发明人： Gwang Hoon Kwag , Pil Sung Kim , Seung Hwon Lee , Hyung Kyu Choi , Hyun Jin Kim
IPC分类号： C08F36/06
CPC分类号： C08C19/44 , C08C19/20 , C08C19/22
摘要： The present invention relates to a preparation method of aromatic organosulfur functionalized 1,4-cis polybutadiene comprising: polymerizing 1,3-butadiene or butadiene derivative in the presence of a specific catalyst in a nonpolar solvent to prepare 1,4-cis polybutadiene; and reacting the resultant polybutadiene with an aromatic organosulfur compound. Such prepared aromatic organosulfur functionalized 1,4-cis polybutadiene is without ultrahigh molecular weight region and, thus, has narrow molecular weight distribution.
摘要翻译：本发明涉及芳香族有机硫官能化1,4-顺式聚丁二烯的制备方法，其特征在于，在特定催化剂存在下，在非极性溶剂中聚合1,3-丁二烯或丁二烯衍生物，制备1,4-顺式聚丁二烯; 并使所得聚丁二烯与芳族有机硫化合物反应。这种制备的芳族有机硫官能化1,4-顺式聚丁二烯不具有超高分子量区域，因此分子量分布窄。

9. 发明授权

US07247695B2 High 1,4-cis polybutadiene-polyurethane copolymer and preparation method thereof 有权
标题翻译：高1,4-顺式聚丁二烯 - 聚氨酯共聚物及其制备方法
公开(公告)号：US07247695B2
公开(公告)日：2007-07-24
申请号：US10827001
申请日：2004-04-19
申请人： Gwang Hoon Kwag , Sam Min Kim , Young Chan Jang , Pil Sung Kim , Seung Hwon Lee , Seung Hwa Lee , A Ju Kim
发明人： Gwang Hoon Kwag , Sam Min Kim , Young Chan Jang , Pil Sung Kim , Seung Hwon Lee , Seung Hwa Lee , A Ju Kim
IPC分类号： C08F36/06 , C08F136/06
CPC分类号： C08L19/006 , C08C19/22 , C08C19/44 , C08F36/04 , C08L9/00 , C08L15/00 , C08F4/545
摘要： Disclosed is a novel high 1,4-cis polybutadiene-polyurethane copolymer and a preparation method thereof. The present invention provides a high 1,4-cis polybutadiene-polyurethane copolymer represented by the following formula 1 and having an average molecular weight of at least 100,000, and a method for preparing the high 1,4-cis polybutadiene-polyurethane copolymer that includes polymerizing 1,3-butadiene or butadiene derivatives with a catalyst comprising a rare earth compound, a halogen-containing compound and an organoaluminum compound in the presence of a non-polar solvent, to prepare a polybutadiene having a high 1,4-cis content of at least 95%; and then introducing a polyurethane group to the polybutadiene. The high 1,4-cis polybutadiene-polyurethane copolymer thus obtained exhibits low cold flow and high affinity to silica or carbon black in admixture as well as excellent in elasticity and abrasion resistance: where l, m, n and o represent the number of repeating unit, 1 is 94 to 99%, m is 0 to 5%, n is 0 to 5%, l+m+n=100%, l/(m+n) is 15 to 100, o is 1 to 100%; and A and Y are C1-C20 alkyl or aryl, respectively.
摘要翻译：公开了一种新型高1,4-顺式聚丁二烯 - 聚氨酯共聚物及其制备方法。本发明提供由下式1表示的平均分子量至少为100,000的高1,4-顺式聚丁二烯 - 聚氨酯共聚物，以及制备高1,4-顺式聚丁二烯 - 聚氨酯共聚物的方法，其包括在非极性溶剂的存在下，用含有稀土类化合物，含卤素化合物和有机铝化合物的催化剂聚合1,3-丁二烯或丁二烯衍生物，制备具有高1,4-顺式含量的聚丁二烯至少95％; 然后将聚氨酯基团引入聚丁二烯。由此获得的高1,4-顺式聚丁二烯 - 聚氨酯共聚物表现出低的冷流和对二氧化硅或炭黑的高亲和性，并且具有优异的弹性和耐磨性：其中l，m，n和o表示重复的数目单元，1为94〜99％，m为0〜5％，n为0〜5％，l + m + n = 100％，l /（m + n）为15〜100，o为1〜100％ ; A和Y分别为C 1 -C 20烷基或芳基。

10. 发明授权

US06908975B2 Method for preparing high 1,4-cis polybutadiene having controlled cold flow 有权
标题翻译：制备具有受控冷流的高1,4-顺式聚丁二烯的方法
公开(公告)号：US06908975B2
公开(公告)日：2005-06-21
申请号：US10653542
申请日：2003-09-02
申请人： Young Chan Jang , Pil Sung Kim , Shin Han , Gwang Hoon Kwag , Seung Hwon Lee
发明人： Young Chan Jang , Pil Sung Kim , Shin Han , Gwang Hoon Kwag , Seung Hwon Lee
IPC分类号： C08F36/06 , C08F136/06
CPC分类号： C08F136/06 , C08F4/545
摘要： The present invention relates to a method for preparing a high 1,4-cis polybutadiene having a controlled cold flow and, more particularly, to a novel method for preparing a high 1,4-cis polybutadiene having a controlled cold flow that involves initiating polymerization of a 1,3-butadiene in the presence of a non-polar solvent using, as a polymerization catalyst, a complex prepared by mixing a neodymium compound with or without a conjugated diene compound, a halogenated organoaluminum compound or a halogenated organic compound, and an organoaluminum compound irrespective of the addition order of the catalyst; and adding an organoborane compound as a cold flow controller of 1,4-cis polybutadiene after a predetermined time of the polymerization. Accordingly, a high 1,4-cis polybutadiene having an efficiently controlled cold flow can be prepared without causing a significant increase in the Mooney viscosity (molecular weight), an odor (bad smell), and a reduction in 1,4-cis content and polymerization yield.
摘要翻译：本发明涉及一种制备具有受控冷流的高1,4-顺式聚丁二烯的方法，更具体地说，涉及一种制备具有控制冷流的高1,4-顺式聚丁二烯的新方法，其涉及引发聚合使用作为聚合催化剂的非极性溶剂存在下的1,3-丁二烯，通过将钕化合物与或不与共轭二烯化合物，卤化有机铝化合物或卤化有机化合物混合制备的络合物和有机铝化合物，而不考虑催化剂的加成顺序; 并在预定的聚合时间之后加入有机硼烷化合物作为1,4-顺式聚丁二烯的冷流控制器。因此，可以制备具有有效控制的冷流的高的1,4-顺式聚丁二烯，而不会导致门尼粘度（分子量），气味（难闻气味）的显着增加和1,4-顺式含量的降低和聚合产率。

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