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1.发明授权Composition and method for color improvement of nitroxyl containing polymers 失效用于含硝酰基聚合物的组合物和颜色改进方法公开(公告)号：US06767949B1
公开(公告)日：2004-07-27
申请号：US10130866
申请日：2002-05-22
IPC分类号： C08L328
CPC分类号： C08K5/32 , C08K5/3435
摘要： The invention relates to a composition comprising, a) at least one oligomer, cooligomer, polymer or copolymer or blends thereof, containing a stable free nitroxyl radical (1); and b) a reducing agent; with the proviso that the composition is essentially free of a polymerizable monomer. A further subject is a process for improving the color of an oligomer, cooligomer, polymer or copolymer or blend thereof, containing a stable free nitroxyl radical (1); by adding a reducing agent to said polymer and heating said mixture to above the glass temperature in case of amorphous polymers or above the melting point in case of crystalline or semi-crystalline polymers
摘要翻译： 本发明涉及一种组合物，其包含a）至少一种含有稳定的游离硝酰基（1）的低聚物，低聚物，聚合物或共聚物或其共混物; 和b）还原剂; 条件是组合物基本上不含可聚合单体。 另一个课题是改进含有稳定的游离硝酰基（1）的低聚物，低聚物，聚合物或共聚物或其共混物的颜色的方法。 通过在无定形聚合物的情况下向所述聚合物中加入还原剂并将所述混合物加热到玻璃化温度以上，或者在结晶或半结晶聚合物的情况下高于熔点
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2.发明申请公开(公告)号：US20060094828A1
公开(公告)日：2006-05-04
申请号：US11299470
申请日：2005-12-12
IPC分类号： C08F293/00
CPC分类号： C08F4/00
摘要： The present invention relates to a composition and process for enhancing the controlled radical polymerization in the presence of nitroxyls and nitroxylethers by adding a chain transfer agent selected from the group consisting of mercaptanes, thioethers and disulfides to the polymerizable mixture. A further subject of the invention is the use of mercaptanes, thioethers and disulfides for increasing rate and yield of controlled radical polymerizations in the presence of a nitroxyl or a nitroxylether.
摘要翻译： 本发明涉及通过将选自硫醇，硫醚和二硫化物的链转移剂加入到可聚合的混合物中，在硝酰氧基和硝酰氧基醚的存在下增强受控自由基聚合的组合物和方法。 本发明的另一个主题是在硝酰基或硝酰基醚的存在下使用硫醇，硫醚和二硫化物来提高受控自由基聚合的速率和产率。
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3.发明授权公开(公告)号：US07323517B2
公开(公告)日：2008-01-29
申请号：US11299470
申请日：2005-12-12
IPC分类号： C08F293/00
CPC分类号： C08F4/00
摘要： The present invention relates to a composition and process for enhancing the controlled radical polymerization in the presence of nitroxyls and nitroxylethers by adding a chain transfer agent selected from the group consisting of mercaptanes, thioethers and disulfides to the polymerizable mixture. A further subject of the invention is the use of mercaptanes, thioethers and disulfides for increasing rate and yield of controlled radical polymerizations in the presence of a nitroxyl or a nitroxylether.
摘要翻译： 本发明涉及通过将选自硫醇，硫醚和二硫化物的链转移剂加入到可聚合的混合物中，在硝酰氧基和硝酰氧基醚的存在下增强受控自由基聚合的组合物和方法。 本发明的另一个主题是在硝酰基或硝酰基醚的存在下使用硫醇，硫醚和二硫化物来提高受控自由基聚合的速率和产率。
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4.发明授权Composition and process for controlled radical polymerization using multifunctional initiator/regulator compounds 失效使用多功能引发剂/调节剂化合物控制自由基聚合的组成和方法公开(公告)号：US06710146B2
公开(公告)日：2004-03-23
申请号：US10406374
申请日：2003-04-03
IPC分类号： C08F404
CPC分类号： C08F2/38 , C08F4/00 , C08K5/34926
摘要： The present invention relates to a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b1) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl and a free radical initiator or b2) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ether. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, the (co)polymers obtainable by this process and the use of multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyls in combination with a free radical initiator, or a multi-functional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ethers for controlled polymerization. In a particularly preferred embodiment at least one additional heating step at a temperature from 140 to 280° C. is applied after polymerization is completed.
摘要翻译： 本发明涉及一种可聚合组合物，其包含a）至少一种烯属不饱和单体和b1）至少一种多官能三嗪基2,2,6,6四甲基哌啶-1-氧基和自由基引发剂或b2）至少一种多官能 三嗪基2,2,6,6四甲基哌啶-1-氧基醚。 本发明的其它方面是聚合烯键式不饱和单体的方法，可通过该方法获得的（共）聚合物和使用多官能三嗪基基2,2,6,6四甲基哌啶-1-氧基与自由基引发剂 ，或用于受控聚合的多官能三嗪基2,2,6,6四甲基哌啶-1-氧基醚。 在特别优选的实施方案中，在聚合完成后，施加140-180℃温度下的至少一个另外的加热步骤。
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公开(公告)号：US07074860B2
公开(公告)日：2006-07-11
申请号：US10381223
申请日：2001-09-18
IPC分类号： C08F293/00
CPC分类号： C08F4/00
摘要： The present invention relates to a composition and process for enhancing the controlled radical polymerization in the presence of nitroxyls and nitroxylethers by adding a chain transfer agent selected from the group consisting of mercaptanes, thioethers and disulfides to the polymerizable mixture. A further subject of the invention is the use of mercaptanes, thioethers and disulfides for increasing rate and yield of controlled radical polymerizations in the presence of a nitroxyl or a nitroxylether.
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6.发明授权Composition and process for controlled radical polymerization using multifunctional initiator/regulator compounds 失效使用多功能引发剂/调节剂化合物控制自由基聚合的组成和方法公开(公告)号：US06573347B1
公开(公告)日：2003-06-03
申请号：US09461927
申请日：1999-12-15
IPC分类号： C08F404
CPC分类号： C08F2/38 , C08F4/00 , C08K5/34926
摘要： The present invention relates to a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b1) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl and a free radical initiator or b2) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ether. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, the (co)polymers obtainable by this process and the use of multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyls in combination with a free radical initiator, or a multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ethers for controlled polymerization. In a particularly preferred embodiment at least one additional heating step at a temperature from 140 to 280° C. is applied after polymerization is completed.
摘要翻译： 本发明涉及一种可聚合组合物，其包含a）至少一种烯属不饱和单体和b1）至少一种多官能三嗪基2,2,6,6四甲基哌啶-1-氧基和自由基引发剂或b2）至少一种多官能 三嗪基2,2,6,6四甲基哌啶-1-氧基醚。 本发明的其它方面是聚合烯键式不饱和单体的方法，可通过该方法获得的（共）聚合物和使用多官能三嗪基基2,2,6,6四甲基哌啶-1-氧基与自由基引发剂 ，或用于受控聚合的多官能三嗪基2,2,6,6四甲基哌啶-1-氧基醚。 在特别优选的实施方案中，在聚合完成后，施加140-180℃温度下的至少一个另外的加热步骤。
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7.发明授权Use of 2,2,6,6 tetraalkylpiperidine-N-oxyl radicals having long alkyl chains as polymerization regulators 失效使用具有长烷基链的2,2,6,6四烷基哌啶-N-氧基作为聚合调节剂公开(公告)号：US06569940B1
公开(公告)日：2003-05-27
申请号：US09720440
申请日：2000-12-22
申请人： Wiebke Wunderlich , Margot Clauss , Michael Roth , Francesco Fuso
发明人： Wiebke Wunderlich , Margot Clauss , Michael Roth , Francesco Fuso
IPC分类号： C07D25106
摘要： The present invention relates to a polymerizable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, b) a radical source capable of starting polymerization of the ethylenically unsaturated monomer or oligomer and c) at least one compound of formula (I), wherein n is 1 or 2; R3, R4, R9, R10 are each independently of one another C1-C18alkyl, C2-C18alkenyl or C2-C18alkinyl; or R3 and R4 and/or R9 and R10 form together with the linking carbon atom a C3-C12cycloakyl radical; R5, R6, R7, R8 are each independently of one another hydrogen, C1-C18alkyl, C2-C18alkenyl or C2C18alkinyl; X is —O—, —O—C(O)—, —NR2— or —NR2—C(O)—; R2 is hydrogen, C1-C18alkyl or phenyl; if n is 1, R1 is C8-C36alkyl, C8-C36alkenyl or C8-C36alkinyl; if n is 2, R1 is C10-C36alkylen, C10-C36alkenylen or C10-C36alkinylen. Further objects of the present invention are a process for polymerization and the use of compounds of formula (I) for the polymerization of ethylenically unsaturated monomers.
摘要翻译： 本发明涉及一种可聚合组合物，其包含a）至少一种烯键式不饱和单体或低聚物，b）能够启动烯属不饱和单体或低聚物聚合的自由基源，和c）至少一种式（I）化合物， 其中n为1或2; R 3，R 4，R 9，R 10各自独立地为C 1 -C 18烷基，C 2 -C 18烯基或C 2 -C 18炔基; 或R 3和R 4和/或R 9和R 10与连接碳原子一起形成C 3 -C 12环烷基; R5，R6，R7，R8各自独立地为氢，C1-C18烷基，C2-C18链烯基或C2C18炔基; X是-O - ， - O-C（O） - ， - NR2-或-NR2-C（O） - ; R2是氢，C1-C18烷基或苯基; 如果n为1，则R1为C8-C36烷基，C8-C36烯基或C8-C36炔基; 如果n为2，则R1为C10-C36亚烷基，C10-C36烯基或C10-C36炔基。 本发明的另外的目的是聚合方法和式（I）化合物用于烯属不饱和单体聚合的方法。
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8.发明授权Use of 2,2,6,6 tetraalkylpiperidine-N-oxyl radicals having long alkyl chains as polymerization regulators 失效使用具有长烷基链的2,2,6,6四烷基哌啶-N-氧基作为聚合调节剂公开(公告)号：US06864313B2
公开(公告)日：2005-03-08
申请号：US10354613
申请日：2003-01-30
申请人： Wiebke Wunderlich , Margot Clauss , Michael Roth , Francesco Fuso
发明人： Wiebke Wunderlich , Margot Clauss , Michael Roth , Francesco Fuso
IPC分类号： C08F2/02 , C08F2/14 , C08F2/16 , C08F2/38 , C08F4/00 , C07D251/06 , C08K5/3492
摘要： The present invention relates to a polymerizable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, b) a radical source capable of starting polymerization of the ethylenically unsaturated monomer or oligomer and c) at least one compound of formula (I) wherein n is 1 or 2 R3, R4, R9, R10 are each independently of one another C1-C18alkyl, C2-C18alkenyl or C2-C18alkinyl; or R3 and R4 and/or R9 and R10 form together with the linking carbon atom a C3-C12cycloalkyl radical; R5, R6, R7, R8 are each independently of one another hydrogen, C1-C18alkyl, C2-C18alkenyl or C2-C18alkinyl; X is —O—, —O—C(O)—, —NR2— or —NR2—C(O)—; R2 is hydrogen, C1-C18alkyl or phenyl; if n is 1, R1 is C8-C38alkyl, C8-C36alkenyl or C8-C36alkinyl if n is 2 R1 is C10-C38alkylen, C10-C36alkenylen or C10-C36alkinylen. Further objects of the present invention are a process for polymerization and the use of compounds of formula I for the polymerization of ethylenically unsaturated monomers.
摘要翻译： 本发明涉及一种可聚合组合物，其包含a）至少一种烯键式不饱和单体或低聚物，b）能够开始烯键式不饱和单体或低聚物聚合的自由基，和c）至少一种式（I）化合物，其中n为1 或2R3，R4，R9，R10各自独立地为C1-C18烷基，C2-C18链烯基或C2-C18链炔基; 或R 3和R 4和/或R 9和R 10与连接碳原子一起形成C 3 -C 12环烷基; R 5，R 6，R 7，R 8各自独立地为氢，C 1 -C 18烷基，C 2 -C 18烯基或C 2 -C 18炔基; X （O） - ，-NR2-或-NR2-C（O） - ; R2是氢，C1-C18烷基或苯基;如果n是1，则R1是C8-C38烷基，C8-C36烯基或 C8-C36炔基是n为2R1的是C10-C38亚烷基，C10-C36烯基或C10-C36炔基。本发明的另一个目的是一种聚合方法和式Ⅰ化合物用于烯属不饱和单体的聚合。
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9.发明授权Nitroxyl derivatives with glycidyl or alkylcarbonyl groups as initiators for radical polymerization 失效具有缩水甘油基或烷基羰基的硝基衍生物作为自由基聚合的引发剂公开(公告)号：US06566468B1
公开(公告)日：2003-05-20
申请号：US09623547
申请日：2000-09-05
申请人： Francesco Fuso , Michael Roth , Wiebke Wunderlich
发明人： Francesco Fuso , Michael Roth , Wiebke Wunderlich
IPC分类号： C08F400
CPC分类号： C08F4/00 , C07D211/46 , C07D211/74 , C07D211/94
摘要： Glycidyl and alkylcarbonyl functional nitroxide radical polymerization initiator compounds of formula (Ia) or (Ib), where R1, R2 and A are as defined within, R3 is a radical of formula (II) where X is phenylene, naphthylene or biphenylene, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; the R12 are independently of each other H or CH3; D is a group a group C(O)—R13 or a group C(O)—R9—C(O)—R13; R13 is C1-C18alkyl and m is a number from 1 to 4, provide polymeric resin products having low polydispersity, polymerization processes that proceed with good monomer to polymer conversion efficiencies and polymers that contain a glycidyl or alkylcarbonyl group.
摘要翻译： 式（Ia）或（Ib）的缩水甘油基和烷基羰基官能的氮氧自由基聚合引发剂化合物，其中R 1，R 2和A如R3中所定义，是式（II）的基团，其中X是亚苯基，亚萘基或亚联苯基，其是未取代的 或被NO 2，卤素，氨基，羟基，氰基，羧基，C 1 -C 4烷氧基，C 1 -C 4烷硫基，C 1 -C 4烷基氨基或二（C 1 -C 4烷基）氨基取代; R 12彼此独立地为H或CH 3; D为 C（O）-R13基或C（O）-R9-C（O）-R13基; R13为C1-C18烷基，m为1至4的数，提供具有低多分散性的聚合物树脂产物， 继续进行良好的单体与聚合物的转化效率以及含有缩水甘油基或烷基羰基的聚合物。
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10.发明申请N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds, their corresponding N-oxides and controlled radical polymerization therewith 失效N-烷氧基-4,4-二氧基 - 多烷基 - 哌啶化合物，它们相应的N-氧化物和受控自由基聚合公开(公告)号：US20060149011A1
公开(公告)日：2006-07-06
申请号：US11364537
申请日：2006-02-28
IPC分类号： C08F4/00 , C07D491/10
CPC分类号： C07D211/94 , C07D491/113 , C07D491/22 , C07D519/00 , C08F2/46 , C08F4/00
摘要： The present invention relates to selected 1-alkoxy-2,2,6,6 tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine derivatives which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) said piperidine derivatives. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of 1-alkoxy-2,2,6,6 tetramethyl piperidine, 1-alkoxy-2,2 diethyl-6,6 dimethyl piperidine and 1-alkoxy-2,6 diethyl-2,3,6 dimethyl piperidine derivatives which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator, as well as a process for polymerization are also subjects of the present invention.
摘要翻译： 本发明涉及选择的1-烷氧基-2,2,6,6四甲基哌啶，1-烷氧基-2,2二乙基-6,6二甲基哌啶和1-烷氧基-2,6-二乙基-2,3,6-二甲基 哌啶衍生物，其在4位被两个形成开链或环状缩酮结构的氧原子取代，所述可聚合组合物包含a）至少一种烯属不饱和单体和b）所述哌啶衍生物。 本发明的另外的方面是使烯键式不饱和单体聚合的方法，以及使用1-烷氧基-2,2,6,6四甲基哌啶，1-烷氧基-2,2二乙基-6,6二甲基哌啶和1- 烷氧基-2,6-二乙基-2,3,6二甲基哌啶衍生物，其在4位被两个氧原子取代，形成用于受控聚合的开链或环状缩酮结构。 中间体N-氧基衍生物，具有烯键式不饱和单体的N-氧基衍生物和自由基引发剂的组合物以及聚合方法也是本发明的主题。
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