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公开(公告)号：US20120059121A1
公开(公告)日：2012-03-08
申请号：US13266917
申请日：2010-04-28
IPC分类号： C08C19/25 , C08K3/36 , C08F136/14 , C08L15/00
CPC分类号： C08C19/25 , B60C1/00 , C08C19/28 , C08F279/02 , C08K3/36 , C08K5/5425 , C08K5/548 , C08F230/08 , C08L15/00 , C08L7/00
摘要： This invention relates to the modification of elastomers by reaction with unsaturated silanes, to the modified elastomers produced and to articles produced by shaping and curing modified elastomer compositions. In a process according to the present, the silane has the formula: R″—CH═CH—C(O)X—Y—SiRaR′(3-a) (I) or R″—C≡C—C(O)X—Y—SiRaR′(3-a) (II) in which R represents a hydrolysable group; R′ represents a hydrocarbyl group having 1 to 6 carbon atoms; a has a value in the range 1 to 3 inclusive; Y represents a divalent organic spacer linkage comprising at least one carbon atom separating the linkage —C(O)X— from the Si atom, X is S or O; and R″ represents hydrogen or a group having an electron withdrawing effect with respect to the —CH═CH— or —C═C— bond; and the silane is reacted with the diene elastomer in the absence of any free radical initiator. This is advantageous because free radical initiators such as peroxides tend to degrade diene elastomers. In addition, safe handling and mixing of peroxides can be difficult for rubber compounders. The grafted diene elastomer produced has improved adhesion to substrates, for example reinforcing cords and fabrics used as reinforcement in rubber articles such as tyres.
摘要翻译： 本发明涉及通过与不饱和硅烷反应对所生产的改性弹性体和通过改性和固化改性弹性体组合物制备的制品来改性弹性体。 在根据本发明的方法中，硅烷具有下式：R“-CH = CH-C（O）X-Y-SiRaR'（3-a）（I）或R”-C≡C-C ）X-Y-SiRaR'（3-a）（II）其中R表示可水解基团; R'表示碳原子数1〜6的烃基。 a的值在1到3的范围内; Y表示包含至少一个碳原子的二价有机间隔键，所述碳原子与Si原子分开连接-C（O）X，X是S或O; 并且R“表示氢或相对于-CH = CH-或-C≡C-键具有吸电子作用的基团; 并且在不存在任何自由基引发剂的情况下，硅烷与二烯弹性体反应。 这是有利的，因为诸如过氧化物的自由基引发剂倾向于降解二烯弹性体。 另外，对于橡胶混合机，过氧化物的安全处理和混合可能是困难的。 生产的接枝二烯烃弹性体具有改善的与基材的粘合性，例如用作橡胶制品如轮胎中的增强材料的增强帘线和织物。
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公开(公告)号：US20120065319A1
公开(公告)日：2012-03-15
申请号：US13318115
申请日：2010-04-28
IPC分类号： C08L43/04 , C08F291/02
CPC分类号： C08F253/00 , B60C1/00 , C08C19/25 , C08C19/28 , C08F279/02 , C08K3/36 , C08K5/5425 , C08K5/548 , C08L51/04 , C08F230/08 , C08L15/00 , C08L7/00 , C08L2666/02
摘要： This invention relates to the modification of elastomers by reaction with unsaturated silanes, to the modified elastomers produced and to articles produced by shaping and curing modified elastomer compositions. It also relates to the use of unsaturated silanes as coupling agents in filled elastomer compositions. In a process according to the present invention, the silane has the formula: R″—CH═CH—C(O)X—Y—SiRaR′(3-a) (I) or R″—C≡C—C(O)X—Y—SiRaR′(3-a) (II) in which R represents a hydrolysable group; R′ represents a hydrocarbyl group having 1 to 6 carbon atoms; a has a value in the range 1 to 3 inclusive; Y represents a divalent organic spacer linkage comprising at least one carbon atom separating the linkage —C(O)X— from the Si atom, X is selected from S or O; and R″ represents hydrogen or a group having an electron withdrawing effect with respect to the —CH═CH— or —C≡C— bond. This provides silanes able to react efficiently with a diene elastomer in the presence of a free radical initiator.
摘要翻译： 本发明涉及通过与不饱和硅烷反应对所生产的改性弹性体和通过改性和固化改性弹性体组合物制备的制品来改性弹性体。 它还涉及在填充的弹性体组合物中使用不饱和硅烷作为偶联剂。 在根据本发明的方法中，硅烷具有下式：R“-CH = CH-C（O）X-Y-SiRaR'（3-a）（I）或R”-C≡C-C O）X-Y-SiRaR'（3-a）（II）其中R表示可水解基团; R'表示碳原子数1〜6的烃基。 a的值在1到3的范围内; Y表示包含至少一个碳原子的二价有机间隔键，所述碳原子与Si原子分开连接-C（O）X，X选自S或O; 并且R“表示氢或相对于-CH = CH-或-C≡C-键具有吸电子作用的基团。 这提供能够在自由基引发剂存在下与二烯弹性体有效反应的硅烷。
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公开(公告)号：US20120283346A1
公开(公告)日：2012-11-08
申请号：US13520859
申请日：2010-12-22
申请人： Michael Backer , Francois De Buyl , Damien Deheunynck , Jean De La Croix Habimana , Vincent Rerat , Valerie Smits
发明人： Michael Backer , Francois De Buyl , Damien Deheunynck , Jean De La Croix Habimana , Vincent Rerat , Valerie Smits
CPC分类号： C08F255/02 , C08F212/14 , C08F230/08 , C08F236/14
摘要： The invention provides a process for grafting silane or silicone functionality onto a polyolefin, comprising reacting the polyolefin with an unsaturated monomer (A) containing an olefinic —C═C— bond or acetylenic —C≡C— bond and a reactive functional group X in the presence of means capable of generating free radical sites in the polyolefin and with an organosilicon compound (B) having a functional group Y which is reactive with the functional group X of the unsaturated monomer (A), characterized in that the unsaturated monomer (A) contains an aromatic ring or a further olefinic double bond or acetylenic unsaturation, the aromatic ring or the further olefinic double bond or acetylenic unsaturation being conjugated with the olefinic —C═C— or acetylenic —C≡C— unsaturation of the unsaturated monomer (A).
摘要翻译： 本发明提供将硅烷或硅氧烷官能度接枝到聚烯烃上的方法，包括使聚烯烃与含有烯烃-C≡C-键或炔属-C≡C-键和反应性官能团X的不饱和单体（A）反应 存在能够在聚烯烃中产生自由基位点的装置和具有与不饱和单体（A）的官能团X反应的官能团Y的有机硅化合物（B）的存在，其特征在于不饱和单体（A ）含有芳环或另外的烯属双键或炔属不饱和键，芳环或其它烯属双键或炔属不饱和键与不饱和单体的烯属-C≡C-或炔属-C≡C-不饱和键相结合（ 一个）。
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公开(公告)号：US09493615B2
公开(公告)日：2016-11-15
申请号：US13520929
申请日：2010-12-22
摘要： The invention provides a composition comprising a polyolefin and a polyorganosiloxane in which at least 50 mole % of the siloxane units are D units as herein defined and which contains at least one unsaturated group, characterized in that the unsaturated group is group of the formula —X—CH═CH—R″ (I) or —X—C≡C—R″ (II), in which X represents a divalent organic linkage having an electron withdrawing effect with respect to the —CH═CH— or —C≡C— bond and/or containing an aromatic ring or a further olefinic double bond or acetylenic unsaturation, the aromatic ring or the further olefinic double bond or acetylenic unsaturation being conjugated with the olefinic unsaturation of —X—CH═CH—R″ or with the acetylenic unsaturation of —X—C≡C—R″ and R″ represents hydrogen or a group having an electron withdrawing effect or any other activation effect with respect to the —CH═CH— or —C≡C— bond.
摘要翻译： 本发明提供包含聚烯烃和聚有机硅氧烷的组合物，其中至少50摩尔％的硅氧烷单元是如本文所定义的D单元，并且含有至少一个不饱和基团，其特征在于不饱和基团是式-X -CH = CH-R“（I）或-X-C≡C-R”（II），其中X表示相对于-CH = CH-或-C≡C具有吸电子效应的二价有机键 C键和/或含有芳环或另外的烯属双键或炔属不饱和键，芳环或其它烯属双键或炔属不饱和键与-X-CH = CH-R“的烯属不饱和键合或与 -X-C≡C-R“和R”的炔属不饱和度表示氢或相对于-CH = CH-或-C≡C-键具有吸电子作用或任何其它活化作用的基团。
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公开(公告)号：US20110190411A1
公开(公告)日：2011-08-04
申请号：US13001668
申请日：2009-07-02
IPC分类号： C08J9/06 , C08F255/02
CPC分类号： C08F255/00 , C08F255/02 , C08F255/08 , C08L51/06 , C08L2666/02 , C09D151/06 , C09J151/06
摘要： The invention relates to a process for grafting hydrolysable silane groups to a polyolefin in which ethylene units, if present, form less than 50% by weight of the total polyolefin. The polyolefin is reacted with an unsaturated silane, having at least one hydrolysable group bonded to Si, or a hydrolysate thereof, in the presence of means capable of generating free radical sites in the polyolefin. The unsaturated silane has the formula R″—CH═CH—Z (I) or R″—C≡C—Z (II) in which Z represents an electron-withdrawing moiety substituted by a —SiRaR′(3-a) group wherein R represents a hydrolysable group; R′ represents a hydrocarbyl group having 1 to 6 carbon atoms; a has a value in the range 1 to 3 inclusive; and R″ represents hydrogen or a group having an electron withdrawing or any other activation effect with respect to the —CH═CH— or —C≡C— bond. The use of an unsaturated silane of the formula R″—CH═CH—Z (I) or R″—C≡C—Z (II) in carrying out the grafting reaction on the polyolefin may give enhanced grafting yield compared to grafting with an olefinically unsaturated silane such as vinyltrimethoxysilane not containing an electron withdrawing moiety Z. The invention permits to provide a silane-modified polyolefin having a high grafting efficiency while limiting/preventing polymer degradation by chain scission. The silane-modified polyolefin can be further reacted with a polar surface, a filler or a polar polymer or reacted on itself to crosslink the polyolefin and obtain enhanced physical properties of the composites made thereof.
摘要翻译： 本发明涉及一种将可水解硅烷基接枝到聚烯烃上的方法，其中乙烯单元（如果存在的话）占总聚烯烃的小于50重量％。 在能够在聚烯烃中产生自由基位点的手段的存在下，聚烯烃与不饱和硅烷反应，所述不饱和硅烷具有与Si结合的至少一个可水解基团或其水解产物。 不饱和硅烷具有式R“-CH = CH-Z（I）或R”-C≡C-Z（II），其中Z表示被-SiRaR'（3-a）基团取代的吸电子部分 其中R表示可水解基团; R'表示碳原子数1〜6的烃基。 a的值在1到3的范围内; 并且R“表示氢或相对于-CH = CH-或-C≡C-键具有吸电子或任何其它活化作用的基团。 在聚烯烃上进行接枝反应时，使用式R“-CH = CH-Z（I）或R”-C≡C-Z（II）的不饱和硅烷可以提高接枝率， 烯属不饱和硅烷如不含吸电子部分Z的乙烯基三甲氧基硅烷。本发明允许提供具有高接枝效率的硅烷改性聚烯烃，同时通过链断裂限制/防止聚合物降解。 硅烷改性的聚烯烃可以进一步与极性表面，填料或极性聚合物反应，或者自身反应以使聚烯烃交联并获得由其制成的复合材料的增强的物理性能。
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公开(公告)号：US20120283388A1
公开(公告)日：2012-11-08
申请号：US13520855
申请日：2010-12-22
申请人： Michael Backer , Thomas Chausse , Francois De Buyl , Damien Deheunynck , Satoshi Onodera , Valerie Smits
发明人： Michael Backer , Thomas Chausse , Francois De Buyl , Damien Deheunynck , Satoshi Onodera , Valerie Smits
IPC分类号： C08F255/02 , C08F8/00
CPC分类号： C08L23/06 , C08F8/42 , C08F290/04 , C08F290/042 , C08F299/08 , C08L23/12 , C08L51/06 , C08L83/10 , C08F10/00 , C08L2666/24 , C08L2666/06 , C08F230/08 , C08F236/14
摘要： The invention provides a process for grafting silicone onto a polyolefin comprising reacting the polyolefin with a silicon compound containing an unsaturated group in the presence of means capable of generating free radical sites in the polyolefin, characterized in that the silicon compound is a branched silicone resin containing at least one group of the formula —X—CH═CH—R″ (I) or —X—C≡C—R″ (II), in which X represents a divalent organic linkage having an electron withdrawing effect with respect to the —CH═CH— or —C≡C-bond and/or containing an aromatic ring or a further olefinic double bond or acetylenic unsaturation, the aromatic ring or the further olefinic double bond or acetylenic unsaturation being conjugated with the olefinic unsaturation of —X—CH═CH—R″ or with the acetylenic unsaturation of —X—C≡C—R″, X being bonded to the branched silicone resin by a C—Si bond, and R″ represents hydrogen or a group having an electron withdrawing effect or any other activation effect with respect to the —CH═CH— or —C□C-bond. The polyolefin is reinforced by grafting the branched silicone resin onto it.
摘要翻译： 本发明提供一种将聚硅氧烷接枝到聚烯烃上的方法，包括使聚烯烃与含有不饱和基团的硅化合物在能够在聚烯烃中产生自由基位点的方式存在下反应，其特征在于硅化合物是含有 至少一个式-X-CH = CH-R“（I）或-X-C≡C-R”（II）的基团，其中X表示具有相对于 -CH = CH-或-C≡C-键和/或含有芳环或另外的烯属双键或炔属不饱和键，所述芳环或其它烯属双键或炔属不饱和键与-X 1的烯属不饱和键 -CH = CH-R“或-X-C≡C-R”的炔属不饱和度，X通过C-Si键与支链硅氧烷树脂键合，R“表示氢或具有吸电子基团 翼效应或相对于-CH = CH-或-C≡C-键的任何其它活化效应。 通过将支化硅树脂接枝到其上来增强聚烯烃。
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公开(公告)号：US09181379B2
公开(公告)日：2015-11-10
申请号：US13520859
申请日：2010-12-22
申请人： Michael Backer , Francois De Buyl , Damien Deheunynck , Jean De La Croix Habimana , Vincent Rerat , Valerie Smits
发明人： Michael Backer , Francois De Buyl , Damien Deheunynck , Jean De La Croix Habimana , Vincent Rerat , Valerie Smits
IPC分类号： C08L23/26 , C08F255/02 , C08F212/14 , C08F230/08
CPC分类号： C08F255/02 , C08F212/14 , C08F230/08 , C08F236/14
摘要： The invention provides a process for grafting silane or silicone functionality onto a polyolefin, comprising reacting the polyolefin with an unsaturated monomer (A) containing an olefinic —C═C— bond or acetylenic —C≡C— bond and a reactive functional group X in the presence of means capable of generating free radical sites in the polyolefin and with an organosilicon compound (B) having a functional group Y which is reactive with the functional group X of the unsaturated monomer (A), characterized in that the unsaturated monomer (A) contains an aromatic ring or a further olefinic double bond or acetylenic unsaturation, the aromatic ring or the further olefinic double bond or acetylenic unsaturation being conjugated with the olefinic —C═C— or acetylenic —C≡C— unsaturation of the unsaturated monomer (A).
摘要翻译： 本发明提供将硅烷或硅氧烷官能度接枝到聚烯烃上的方法，包括使聚烯烃与含有烯烃-C≡C-键或炔属-C≡C-键和反应性官能团X的不饱和单体（A）反应 存在能够在聚烯烃中产生自由基位点的装置和具有与不饱和单体（A）的官能团X反应的官能团Y的有机硅化合物（B）的存在，其特征在于不饱和单体（A ）含有芳环或另外的烯属双键或炔属不饱和键，芳环或其它烯属双键或炔属不饱和键与不饱和单体的烯属-C≡C-或炔属-C≡C-不饱和键相结合（ 一个）。
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公开(公告)号：US08569417B2
公开(公告)日：2013-10-29
申请号：US13001668
申请日：2009-07-02
IPC分类号： C08F255/00 , C08F255/02 , C08F8/12 , C08F8/42
CPC分类号： C08F255/00 , C08F255/02 , C08F255/08 , C08L51/06 , C08L2666/02 , C09D151/06 , C09J151/06
摘要： The invention relates to a process for grafting hydrolysable silane groups to a polyolefin in which ethylene units, if present, form less than 50% by weight of the total polyolefin. The polyolefin is reacted with an unsaturated silane, having at least one hydrolysable group bonded to Si, or a hydrolysate thereof, in the presence of means capable of generating free radical sites in the polyolefin. The unsaturated silane has the formula R″—CH═CH—Z (I) or R″—C≡C—Z (II) in which Z represents an electron-withdrawing moiety substituted by a —SiRaR′(3-a) group wherein R represents a hydrolysable group; R′ represents a hydrocarbyl group having 1 to 6 carbon atoms; a has a value in the range 1 to 3 inclusive; and R″ represents hydrogen or a group having an electron withdrawing or any other activation effect with respect to the —CH═CH— or —C≡C— bond. The use of an unsaturated silane of the formula R″—CH═CH—Z (I) or R″—C≡C—Z (II) in carrying out the grafting reaction on the polyolefin may give enhanced grafting yield compared to grafting with an olefinically unsaturated silane such as vinyltrimethoxysilane not containing an electron withdrawing moiety Z. The invention permits to provide a silane-modified polyolefin having a high grafting efficiency while limiting/preventing polymer degradation by chain scission. The silane-modified polyolefin can be further reacted with a polar surface, a filler or a polar polymer or reacted on itself to crosslink the polyolefin and obtain enhanced physical properties of the composites made thereof.
摘要翻译： 本发明涉及一种将可水解硅烷基接枝到聚烯烃上的方法，其中乙烯单元（如果存在的话）占总聚烯烃的小于50重量％。 在能够在聚烯烃中产生自由基位点的手段的存在下，聚烯烃与不饱和硅烷反应，所述不饱和硅烷具有与Si结合的至少一个可水解基团或其水解产物。 不饱和硅烷具有式R“-CH = CH-Z（I）或R”C = CZ（II），其中Z表示被-SiRaR'（3-a）基团取代的吸电子部分 其中R表示可水解基团; R'表示碳原子数1〜6的烃基。 a的值在1到3的范围内; R“表示氢或相对于-CH = CH-或-C = C-键具有吸电子或任何其它活化作用的基团。 在聚烯烃上进行接枝反应时，使用式R'-CH = CH-Z（I）或R“C = CZ（II）的不饱和硅烷可以提高接枝率， 烯属不饱和硅烷如不含吸电子部分Z的乙烯基三甲氧基硅烷。本发明允许提供具有高接枝效率的硅烷改性聚烯烃，同时通过链断裂限制/防止聚合物降解。 硅烷改性的聚烯烃可以进一步与极性表面，填料或极性聚合物反应，或者自身反应以使聚烯烃交联并获得由其制成的复合材料的增强的物理性能。
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公开(公告)号：US20120283362A1
公开(公告)日：2012-11-08
申请号：US13520929
申请日：2010-12-22
摘要： The invention provides a composition comprising a polyolefin and a polyorganosiloxane in which at least 50 mole % of the siloxane units are D units as herein defined and which contains at least one unsaturated group, characterized in that the unsaturated group is group of the formula —X—CH═CH—R″ (I) or —X—C≡C—R″ (II), in which X represents a divalent organic linkage having an electron withdrawing effect with respect to the —CH═CH— or —C≡C— bond and/or containing an aromatic ring or a further olefinic double bond or acetylenic unsaturation, the aromatic ring or the further olefinic double bond or acetylenic unsaturation being conjugated with the olefinic unsaturation of —X—CH═CH—R″ or with the acetylenic unsaturation of —X—C≡C—R″ and R″ represents hydrogen or a group having an electron withdrawing effect or any other activation effect with respect to the —CH═CH— or —C≡C— bond.
摘要翻译： 本发明提供包含聚烯烃和聚有机硅氧烷的组合物，其中至少50摩尔％的硅氧烷单元是如本文所定义的D单元，并且含有至少一个不饱和基团，其特征在于不饱和基团是式-X -CH = CH-R“（I）或-X-C≡C-R”（II），其中X表示相对于-CH = CH-或-C≡C具有吸电子效应的二价有机键 C键和/或含有芳环或另外的烯属双键或炔属不饱和键，芳环或其它烯属双键或炔属不饱和键与-X-CH = CH-R“的烯属不饱和键合或与 -X-C≡C-R“和R”的炔属不饱和度表示氢或相对于-CH = CH-或-C≡C-键具有吸电子作用或任何其它活化作用的基团。
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公开(公告)号：US20110046272A1
公开(公告)日：2011-02-24
申请号：US12745213
申请日：2008-11-28
申请人： Valerie Smits , Michael Backer , Sebastien Grofils , Thierry Materne , Laurence Stelandre , Randall Schmidt , Steven Swier , Thomas Chaussee
发明人： Valerie Smits , Michael Backer , Sebastien Grofils , Thierry Materne , Laurence Stelandre , Randall Schmidt , Steven Swier , Thomas Chaussee
CPC分类号： B60C1/00 , C08K3/36 , C08K5/5419 , C08K5/5425 , C08K5/548 , C08L9/00 , C08L9/06 , C08L21/00 , C08L83/04 , C08L2666/02 , C08L83/00
摘要： The present invention relates to a curable rubber composition comprising an organic elastomer, a filler and at least one curing agent for the elastomer. Such curable rubber compositions are widely used in the production of cured rubber articles, such as tyres, belts and hoses. The composition contains a branched silicone resin having Si-bonded hydroxyl groups or azo groups. This may lead to a reduction in the mixing energy required for processing, particularly in the energy required in the first (non-productive) mixing phase to give good dispersion of the filler in the organic elastomer. Use of the branched silicone resin can also accelerate cure (vulcanization), thus reducing the required cure time or reducing the amount of cure accelerator required.
摘要翻译： 本发明涉及包含有机弹性体，填料和至少一种用于弹性体的固化剂的可固化橡胶组合物。 这种可固化橡胶组合物广泛用于生产固化橡胶制品，如轮胎，皮带和软管。 该组合物含有具有Si键合的羟基或偶氮基团的支链硅树脂。 这可能导致加工所需的混合能量的降低，特别是在第一（非生产性）混合阶段所需的能量中，以使填料在有机弹性体中得到良好的分散。 使用支化硅树脂也可以加速固化（硫化），从而减少所需的固化时间或减少所需的固化促进剂的量。
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