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1. 发明授权

US4758639A Process for production of vinyl polymer 失效
标题翻译：乙烯基聚合物生产工艺
公开(公告)号：US4758639A
公开(公告)日：1988-07-19
申请号：US94020
申请日：1987-09-03
申请人： Shunichi Koyanagi , Hajime Kutamura , Toshihide Shimizu , Ichiro Kaneko
发明人： Shunichi Koyanagi , Hajime Kutamura , Toshihide Shimizu , Ichiro Kaneko
IPC分类号： C08F2/00 , C08F2/18 , C08F2/22 , C08F2/44
CPC分类号： C08F2/004
摘要： A process for production of a vinyl polymer by suspension polymerization or emulsion polymerization of at least one kind of vinyl monomer in an aqueous medium is disclosed.In this process, the polymerization is carried out in a polymerizer, the inner wall surface and portions of the auxiliary equipment thereof which may come into contact with the monomer during polymerization having a surface roughness of not greater than 5 .mu.m and being previously coated with a scaling preventive comprising at least one selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated .pi. bonds. According to this process, scaling on the inner wall surface of a polymerizer, etc. during polymerization can be prevented effectively and surely.
摘要翻译：公开了通过在水性介质中悬浮聚合或至少一种乙烯基单体的乳液聚合制备乙烯基聚合物的方法。在该方法中，聚合反应在聚合反应器中进行，其内壁表面及其辅助设备的部分可在聚合过程中与单体接触，表面粗糙度不大于5μm，并预先涂覆防垢剂包含选自染料，颜料和具有至少5个共轭π键的芳族或杂环化合物中的至少一种。根据该方法，可以有效且可靠地防止聚合反应器内壁表面的缩小。

2. 发明授权

US4528336A Method for preventing polymer scale deposition in polymerization of ethylenically unsaturated monomers 失效
标题翻译：防止烯属不饱和单体聚合中聚合物垢沉积的方法
公开(公告)号：US4528336A
公开(公告)日：1985-07-09
申请号：US361040
申请日：1982-03-23
申请人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Ichiro Kaneko
发明人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Ichiro Kaneko
IPC分类号： C08F2/00 , C08F2/12 , C08F2/20 , C08F14/06
CPC分类号： C08F2/004
摘要： The invention provides a very efficient method with highly durable effect for preventing polymer scale deposition on the reactor walls and other surfaces coming into contact with the monomer during polymerization of an ethylenically unsaturated polymerizable monomer in an aqueous medium such as in the suspension polymerization of vinyl chloride. The method comprises coating the reactor walls, prior to polymerization, with a novel coating material which is a condensation product obtained by the condensation reaction of an aromatic amine compound such as aniline and an aromatic nitro compound such as nitrobenzene in the presence of a mineral acid and a specified condensation catalyst. It is sometimes preferable that the condensation product is basified or treated with an alkali or ammonium compound to be imparted with a modified solubility behavior.
摘要翻译：本发明提供了一种非常有效的方法，其具有高度耐久的效果，用于防止聚合物垢沉积在反应器壁和其它与单体接触的表面中，所述表面在烯属不饱和可聚合单体在水性介质中聚合期间，例如在氯乙烯的悬浮聚合中。该方法包括在聚合之前用反应器壁涂覆新的涂料，该涂料是通过在无机酸存在下芳族胺化合物如苯胺和芳族硝基化合物如硝基苯的缩合反应获得的缩合产物和指定的缩合催化剂。有时优选将缩合产物碱化或用碱或铵化合物处理以赋予改性的溶解行为。

3. 发明授权

US4757124A Process for production of vinyl chloride polymer 失效
标题翻译：生产氯乙烯聚合物的方法
公开(公告)号：US4757124A
公开(公告)日：1988-07-12
申请号：US76996
申请日：1987-07-21
申请人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Ichiro Kaneko
发明人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Ichiro Kaneko
IPC分类号： C08F14/06 , C08F2/00 , C08F2/18 , C08F4/06 , C08F2/22 , C08F2/44
CPC分类号： C08F2/004
摘要： This process is a process for production of a vinyl chloride polymer by suspension polymerization or emulsion polymerization of vinyl chloride monomer or a mixture of vinyl chloride monomer with a vinyl monomer copolymerizable with said vinyl chloride monomer in an aqueous medium, characterized in that the polymerization is carried out in a polymerizer, the inner wall surface and portions of the auxiliary equipment thereof which may come into contact with the monomer during polymerization being previously coated with a scaling preventive comprising at least one selected from dyes, pigments and aromatic or heterocyclic compounds having at least 5 conjugated .pi. bonds, while controlling the chloride ion concentration in the reaction mixture to not higher than 100 ppm. According to said process, scaling onto the inner wall surface of a polymerizer, etc. during polymerization can be prevented effectively and surely.
摘要翻译：该方法是通过氯乙烯单体或氯乙烯单体与可与所述氯乙烯单体在水性介质中共聚的乙烯基单体的混合物的悬浮聚合或乳液聚合制备氯乙烯聚合物的方法，其特征在于聚合是在聚合反应器中进行的内壁表面及其辅助设备的部分可在聚合期间与单体接触，预先涂覆防垢剂，其包含选自染料，颜料和芳族或杂环化合物中的至少一种，其具有最少5个共轭π键，同时将反应混合物中的氯离子浓度控制在不高于100ppm。根据所述方法，能够有效且可靠地防止在聚合反应期间缩聚到聚合反应器内壁表面等。

4. 发明授权

US4173696A Method for the polymerization of vinyl monomers 失效
标题翻译：乙烯基单体聚合方法
公开(公告)号：US4173696A
公开(公告)日：1979-11-06
申请号：US871249
申请日：1978-01-23
申请人： Shunichi Koyanagi , Niichiro Hasegawa , Toshihide Shimizu , Sensaku Katusima , Ichiro Kaneko
发明人： Shunichi Koyanagi , Niichiro Hasegawa , Toshihide Shimizu , Sensaku Katusima , Ichiro Kaneko
IPC分类号： C08F2/44 , C08F20060101 , C08F2/00 , C08F2/18 , C08F2/38 , C08F2/02 , C08F2/22
CPC分类号： C08F2/004
摘要： A novel and improved method for polymerizing a vinyl monomer in a polymerization reactor is provided. The inner walls of the polymerization reactor and other surfaces coming into contact with the monomer are coated with an aqueous liquid containing at least one alkali metal or ammonium salt of an anionic dye of the sulfonic carboxylic acid form and having a pH value adjusted not to exceed 7 by aid of a pH adjusting agent, and the thus coated surfaces are dried with heat before the polymerization is conducted. The method serves to greatly reduce the deposition of polymer scale on those surfaces and, consequently, improve the productivity as well as the quality of polymer product.
摘要翻译：提供了一种在聚合反应器中聚合乙烯基单体的新颖和改进的方法。聚合反应器的内壁和与单体接触的其它表面涂覆有含有至少一种磺酸羧酸形式的阴离子染料的碱金属盐或铵盐的水溶液，其pH值调节不超过通过pH调节剂，并且在进行聚合之前将这样涂覆的表面加热干燥。该方法用于大大降低聚合物垢在这些表面上的沉积，从而提高聚合物产品的生产率和质量。

5. 发明授权

US4090015A Method for polymerizing dienic monomers 失效
标题翻译：聚合二烯单体的方法
公开(公告)号：US4090015A
公开(公告)日：1978-05-16
申请号：US818756
申请日：1977-07-25
申请人： Shunichi Koyanagi , Niichiro Hasegawa , Toshihide Shimizu , Ichiro Kaneko , Sensaku Katsushima
发明人： Shunichi Koyanagi , Niichiro Hasegawa , Toshihide Shimizu , Ichiro Kaneko , Sensaku Katsushima
IPC分类号： C08F2/00 , C08F2/22 , C08F2/24 , C08F12/08 , C08F279/04
CPC分类号： C08F2/004
摘要： In the emulsion polymerization of a dienic monomer or a mixture containing a dienic monomer and at least one other copolymerizable monomer in an aqueous medium, the deposition of polymer scale on the inner walls of the polymerization reactor and other surfaces in contact with the monomer or monomeric mixture can be remarkably reduced or prevented by providing coating layers of an organopolysiloxane on those surfaces, prior to the polymerization, by applying the organopolysiloxane directly to the surfaces or by applying one or a mixture of hydrolyzable organosilanes to the surfaces, followed by hydrolysis-condensation of the silanes, to form the organopolysiloxane in situ.
摘要翻译：在含水介质中的二烯单体或含有二烯单体和至少一种其它可共聚单体的混合物的乳液聚合中，在聚合反应器的内壁和与单体或单体接触的其它表面上沉积聚合物垢通过在聚合前在这些表面上提供有机聚硅氧烷的涂层，通过将有机聚硅氧烷直接施加在表面上或者通过将表面上施加一种或可水解有机硅烷的混合物，然后进行水解缩合，可以显着降低或防止混合物的硅烷，原位形成有机聚硅氧烷。

6. 发明授权

US3945958A Method for suspension-polymerizing vinyl chloride 失效
标题翻译：悬浮聚合氯乙烯的方法
公开(公告)号：US3945958A
公开(公告)日：1976-03-23
申请号：US475052
申请日：1974-05-31
申请人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu
发明人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu
IPC分类号： C08F14/06 , C08F2/20
CPC分类号： C08F14/06
摘要： When vinyl chloride or a mixture of monomers containing vinyl chloride as its main component is subjected to suspension-polymerization, in the presence of a polymerization initiator, employing as a suspending agent an aqueous medium consisting of two kinds of water-soluble cellulose ethers, the 2% aqueous solution of one of which has a viscosity of at most 100 cps at 20.degree.C, and that of the other has a viscosity of at least 400 cps at 20.degree.C, the product obtained will be a porous polymer superior not only in uniformity of particle size, and absorptivity of plasticizers and liquid heat-stabilizers but also in processability.
摘要翻译：当氯乙烯或含有氯乙烯作为其主要成分的单体的混合物进行悬浮聚合时，在聚合引发剂的存在下，使用由两种水溶性纤维素醚组成的水性介质作为悬浮剂，其中之一的2％水溶液在20℃下的粘度至多为100cps，另一种的水溶液在20℃时的粘度至少为400cps，所得产品将不仅优于多孔聚合物颗粒尺寸的均匀性和增塑剂和液体热稳定剂的吸收性，而且在加工性方面。

7. 发明授权

US4180634A Polymerizing vinyl chloride with lowering of scale formation 失效
标题翻译：聚合氯乙烯，降低水垢形成
公开(公告)号：US4180634A
公开(公告)日：1979-12-25
申请号：US888166
申请日：1978-03-20
申请人： Shunichi Koyanagi , Toshihide Shimizu , Kenji Fushimi
发明人： Shunichi Koyanagi , Toshihide Shimizu , Kenji Fushimi
IPC分类号： C08F2/00 , C08F2/18 , C08F14/06 , C08F18/08
CPC分类号： C08F2/005 , C08F14/06
摘要： A method for polymerizing vinyl chloride in an aqueous suspension wherein polymer scale is prevented from depositing on walls and other surfaces in contact with monomer in a polymerization reactor. According to the method, one or more compounds selected from iodine salts of alkali metals and alkaline earth metals are added to the polymerization mixture. The effect of this method can be enhanced synergistically by coating a polar organic compound or an organic dye over the surfaces in contact with the monomer.
摘要翻译：一种在水性悬浮液中聚合氯乙烯的方法，其中防止聚合物垢在聚合反应器中沉积在与单体接触的壁和其它表面上。根据该方法，将一种或多种选自碱金属和碱土金属的碘盐的化合物加入到聚合混合物中。通过在与单体接触的表面上涂布极性有机化合物或有机染料，可以协同地提高该方法的效果。

8. 发明授权

US4105839A Method for polymerizing ethylenically unsaturated monomers in order to eliminate polymer deposition 失效
标题翻译：聚合烯属不饱和单体以消除聚合物沉积的方法
公开(公告)号：US4105839A
公开(公告)日：1978-08-08
申请号：US713894
申请日：1976-08-12
申请人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Kenji Fushimi
发明人： Shunichi Koyanagi , Hajime Kitamura , Toshihide Shimizu , Kenji Fushimi
IPC分类号： C08F236/10 , C08F2/00 , C08F2/18 , C08F2/44 , C08F214/08 , C08F216/06 , C08F2/16
CPC分类号： C08F2/004
摘要： In the polymerization of at least one ethylenically unsaturated monomer other than vinyl chloride, deposition of polymer scale on the inner walls of a polymerization reactor and other surfaces coming into contact with the monomer is effectively prevented (regardless of the type of polymerization used, so long as it takes place in a heterogeneous phase) by coating the surfaces of the reactor with at least one compound selected from organic electron donor compounds and organic electron-acceptor compounds prior to polymerization; the compound or compounds having been or being brought into contact with an oxidizing agent, a reducing agent, an acid or a base, or having been or being irradiated with ultraviolet light.
摘要翻译：在除了氯乙烯之外的至少一种烯键式不饱和单体的聚合中，聚合物垢在聚合反应器的内壁和与单体接触的其它表面上的沉积被有效地防止（不管使用的聚合物类型如何长因为它发生在非均相中）通过在聚合之前用至少一种选自有机电子给体化合物和有机电子受体化合物的化合物涂覆反应器的表面; 已经或已经与氧化剂，还原剂，酸或碱接触的化合物或化合物，或已被或被紫外线照射的化合物或化合物。

9. 发明授权

US5034478A Method of preventing polymer scale formation 失效
公开(公告)号：US5034478A
公开(公告)日：1991-07-23
申请号：US446699
申请日：1989-12-06
申请人： Toshihide Shimizu , Ichiro Kaneko , Mikio Watanabe
发明人： Toshihide Shimizu , Ichiro Kaneko , Mikio Watanabe
IPC分类号： C08F2/00
CPC分类号： C08F2/004
摘要： A method of preventing polymer scale deposition in polymerization of a monomer having an ethylenically double bond, wherein said polymerization is carried out in a polymerization vessel in which its inner wall surface has been previously coated with a coating solution comprising:(A) a condensate of a phenolic hydroxy group-containing compound,(B) at least one member selected from the group consisting of metal compounds and inorganic colloids, and(C) at least one member selected from the group consisting of dyes and pigments. This method makes it possible to prevent polymer scale deposition regardless of polymerization conditions such as the kind of monomers, the type of polymerization vessel, etc.

10. 发明授权

US4708890A Method for preventing polymer scale deposition on the reactor walls in the polymerization of ethylenically unsaturated monomers 失效
标题翻译：防止烯属不饱和单体聚合反应器壁上的聚合物垢沉积的方法
公开(公告)号：US4708890A
公开(公告)日：1987-11-24
申请号：US886721
申请日：1986-07-18
申请人： Toshihide Shimizu , Ichiro Kaneko , Mikio Watanabe , Yoshiteru Shimakura
发明人： Toshihide Shimizu , Ichiro Kaneko , Mikio Watanabe , Yoshiteru Shimakura
IPC分类号： C08F2/00 , C08F2/16 , C08F14/00 , C08F14/06
CPC分类号： C08F2/004
摘要： The invention provides an efficient method for preventing polymer scale deposition on the reactor walls in the suspension or emulsion polymerization of an ethylenically unsaturated monomer, e.g. vinyl chloride and styrene, by coating the reactor walls, prior to introduction of the polymerization mixture, with an aqueous coating solution containing (a) a silicic acid compound, e.g. colloidal silicic acid, and (b) a phosphorous compound, e.g. phytic acid and polyphosphoric acid, in a specified weight proportion followed by drying.
摘要翻译：本发明提供了一种在烯属不饱和单体的悬浮或乳液聚合中防止聚合物垢在反应器壁上沉积的有效方法，例如，氯乙烯和苯乙烯，通过在引入聚合混合物之前用包含（a）硅酸化合物的水性涂料溶液涂覆反应器壁。胶体硅酸，和（b）磷化合物，例如，植酸和多磷酸，以规定的重量比例然后干燥。

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