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21. 发明申请

US20110060157A1 APPARATUS AND METHODS FOR CONTROLLED RADICAL POLYMERIZATION 有权
标题翻译：控制辐射聚合的装置和方法
公开(公告)号：US20110060157A1
公开(公告)日：2011-03-10
申请号：US12946895
申请日：2010-11-16
申请人： David M. Glaser , Roderick Coffey , John G. Woods , Anthony F. Jacobine
发明人： David M. Glaser , Roderick Coffey , John G. Woods , Anthony F. Jacobine
IPC分类号： C07C67/347
CPC分类号： C08F220/18 , B01J14/005 , B01J16/005 , B01J19/0066 , B01J19/1881 , B01J2219/00063 , B01J2219/00069 , B01J2219/00094 , B01J2219/00162 , B01J2219/002 , B01J2219/00213 , B01J2219/00231 , B01J2219/00238 , C08F2/00 , C08F293/005 , C08F2438/01
摘要： A method of conducting controlled radical polymerization, including: (a) providing a mixture of at least one monomer; at least one monomer solvent; at least one compound metal coordinating capable; and at least one initiator; (b) directing the mixture at a rate over a solid catalyst surface contained in an external chamber to the vessel, the catalyst including a metal or metal compound capable of at least two oxidation states; (c) monitoring the reaction vessel temperature; (d) adjusting the flow rate when the temperature is outside a selected temperature range; and (e) allowing the polymerization to proceed to desired conversion level.
摘要翻译：一种进行受控自由基聚合的方法，包括：（a）提供至少一种单体的混合物; 至少一种单体溶剂; 至少一种配位的复合金属; 和至少一个引发剂; （b）以混合物的速率将包含在外部室中的固体催化剂表面的速率引导至容器，所述催化剂包括能够具有至少两种氧化态的金属或金属化合物; （c）监测反应容器的温度; （d）当温度在选定的温度范围之外时调节流量; 和（e）允许聚合进行到所需的转化水平。

22. 发明授权

US5459173A Stabilizer system for thiol-ene and thiol-nene compositions 失效
标题翻译：稳定剂体系，用于硫醇和烯烃组合物
公开(公告)号：US5459173A
公开(公告)日：1995-10-17
申请号：US81456
申请日：1993-06-22
申请人： David M. Glaser , Anthony F. Jacobine , Paul J. Grabek
发明人： David M. Glaser , Anthony F. Jacobine , Paul J. Grabek
IPC分类号： C08K5/13 , C08G75/04 , C08G75/14 , C08K5/17 , C08L81/04 , C08K5/08
CPC分类号： C08G75/045
摘要： Stable thiol-ene compositions are provided which comprise a polythiol, a polyene and a stabilizer system comprising an alkenyl substituted phenolic compound having a formula: ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 are independently selected from the group consisting of H, OR, a C.sub.1 -C.sub.8 alkyl, substituted alkyl, alkenyl or substituted alkenyl, a C.sub.6 -C.sub.20 aryl or substituted aryl, or a cyano group; R.sup.4 is H, R, OR, halogen, COR, COOR, or SR; R.sup.5 is OH, OR, OCOR, OCOOR, OCONHR, or OTMS; R is a C.sub.1 -C.sub.6 alkyl, a cycloalkyl, or a C.sub.6 -C.sub.20 caryl or substituted aryl; x and y are 1, 2, or 3; z is 0, 1, or 2; and x+y+z=2, 3, or 4; or a formula: ##STR2## where x, y, z, w, R.sup.1 R.sup.2 R.sup.3, R.sup.4 and R.sup.5 are defined as above, except that x+y+z=2-6, and R.sup.6 is CH.sub.2, C(CH.sub.3).sub.2, O, S, or SO.sub.2 ; and one or more compounds selected from the group consisting of a free radical scavenger, a hindered phenolic antioxidant and a hydroxylamine derivative.
摘要翻译：提供了稳定的硫醇 - 烯组合物，其包含多硫醇，多烯和包含具有下式的烯基取代的酚化合物的稳定剂体系：其中R1，R2和R3独立地选自H，OR， C1-C8烷基，取代的烷基，烯基或取代的烯基，C6-C20芳基或取代的芳基或氰基; R4是H，R，OR，卤素，COR，COOR或SR; R5是OH，OR，OCOR，OCOOR，OCONHR或OTMS; R是C 1 -C 6烷基，环烷基或C 6 -C 20甲酰基或取代的芳基; x和y分别为1,2或3; z为0,1或2; x + y + z = 2,3或4; 或者式：其中x，y，z，w，R 1，R 2，R 3和R 4如上所定义，除了x + y + z = 2-6，并且R 6是CH 2，C（CH 3）2 ，O，S或SO 2; 和一种或多种选自自由基清除剂，受阻酚抗氧化剂和羟胺衍生物的化合物。

23. 发明授权

US5371181A Thiol-ene compositions with improved cure speed retention 失效
标题翻译：具有改进固化速度保持性的硫醇烯组合物
公开(公告)号：US5371181A
公开(公告)日：1994-12-06
申请号：US81078
申请日：1993-06-22
申请人： David M. Glaser , Anthony F. Jacobine , Paul J. Grabek
发明人： David M. Glaser , Anthony F. Jacobine , Paul J. Grabek
IPC分类号： B29C67/00 , C03C25/10 , C07D263/42 , C08F2/50 , C08F6/02 , C08F8/34 , C08F8/42 , C08G65/332 , C08G73/02 , C08G75/04 , C09D4/00 , G02B6/44 , G03F7/00 , G03F7/027 , C08G85/00 , C08G75/14
CPC分类号： C03C25/106 , B29C67/0066 , C07D263/42 , C08F6/02 , C08G65/332 , C08G73/028 , C08G75/045 , C09D4/00 , G02B6/443 , G03F7/0037 , G03F7/0275
摘要： A treatment method for polythiol compounds used in thiol-ene formulations, especially formulations employing norbornene resins, significantly improves cure speed retention on aging of thiol-ene formulations which include hydroxylamine salts, such as N-nitrosoarylhydroxylamine aluminum salts, as shelf-life stabilizers. The treatment comprises contacting the polythiol with an amphoteric treating agent selected from the group consisting of silicated magnesium oxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, barium oxide, and barium hydroxide, and then separating the resin from the treating agent prior to mixture with a polyene to form a thiol-ene composition. In formulations employing phenolic compounds having an alkenyl group in conjugation with the phenyl group thereof as shelf-life co-stabilizers the treatment method also significantly enhances the shelf-life stability of the formulation compared to formulations made from untreated polythiol.
摘要翻译：用于硫醇烯制剂的多硫醇化合物的处理方法，特别是使用降冰片烯树脂的制剂，显着地改善了包含羟胺盐（例如N-亚硝基芳基羟胺铝盐）作为保质期稳定剂的硫醇 - 烯制剂老化时的固化速度保持。处理包括使多硫醇与选自硅酸镁，氧化镁，氢氧化镁，氧化钙，氢氧化钙，氧化钡和氢氧化钡的两性处理剂接触，然后将树脂从处理剂中分离出来与多烯混合以形成硫醇 - 烯组合物。在使用具有与其苯基缀合的烯基的酚类化合物作为保质期共稳定剂的制剂中，与未处理的多硫醇制备的制剂相比，处理方法也显着提高了制剂的保质期稳定性。

24. 发明授权

US5034490A Curable norbornenyl functional silicone formulations 失效
标题翻译：可固化的降冰片烯功能硅氧烷配方
公开(公告)号：US5034490A
公开(公告)日：1991-07-23
申请号：US315431
申请日：1989-02-24
申请人： Anthony F. Jacobine , David M. Glaser , Steven T. Nakos
发明人： Anthony F. Jacobine , David M. Glaser , Steven T. Nakos
IPC分类号： C08L83/05 , C08G75/04 , C08G77/20 , C08G77/38 , C08L83/04 , C08L83/06 , C08L83/07 , C08L83/08
CPC分类号： C08L83/04 , C08G75/045 , C08G77/20 , C08G77/38 , C08L83/06 , C08L83/08 , C08G77/12
摘要： A composition cureable to a solid crosslinked polyorganosiloxane comprises:a) a norbornene functional silicone prepolymer having a plurality of groups of the formula: ##STR1## bound to silicone atoms thereof, where R is H or methyl, R.sup.1 is a direct bond of --C(.dbd.O)O-- and R.sup.4 is ethylene, ethenylene, propylene or propenylene,b) a coreactive silicone prepolymer selected from SiH functional silicones, and alkylthiol functional silicones, said polyorganosiloxanes (a) and (b) being present in an equivalent ratio of between 2:1 and 1:2 norbornene to silicon hydride or alkyl thiol groups, andc) an effective amount of a hydrosilation or thiol-ene cure catalyst, respectively.
摘要翻译：可固化至固体交联聚有机硅氧烷的组合物包括：a）降冰片烯官能的硅氧烷预聚物，其具有与下列结合的多个下式的基团：其硅氧烷原子，其中R为H或甲基，R 1为-C （= O）O-和R4是亚乙基，亚乙烯基，丙烯或亚丙烯基，b）选自SiH官能硅氧烷和烷基硫醇官能硅氧烷的共聚活性硅氧烷预聚物，所述聚有机硅氧烷（a）和（b）以 2：1和1：2降冰片烯分别与硅氢化物或烷基硫醇基团，和c）分别有效量的硅氢化或硫醇 - 固化催化剂。

25. 发明授权

US4808638A Thiolene compositions on based bicyclic 'ene compounds 失效
标题翻译：基于双环“烯化合物的硫醇组合物
公开(公告)号：US4808638A
公开(公告)日：1989-02-28
申请号：US99676
申请日：1987-09-21
申请人： Walter J. Steinkraus , John Woods , John M. Rooney , Anthony F. Jacobine , David M. Glaser
发明人： Walter J. Steinkraus , John Woods , John M. Rooney , Anthony F. Jacobine , David M. Glaser
IPC分类号： C08G75/04
CPC分类号： C08G75/045
摘要： A curable thiol-ene formulation comprising(a) a polythiol(b) a 'ene compound having a plurality of groups of the formula: ##STR1## where Q is CH.sub.2, CHCH.sub.3, C(Ch.sub.3).sub.2, O, S, NR.sup.1 or SO.sub.2 R.sup.1 is H or alkyl, and m is 0-10, and(c) an effective amount of a free radical initiator.
摘要翻译：一种可固化的硫醇烯制剂，其包含（a）多硫醇（b）具有下式的多个基团的烯化合物：其中Q是CH 2，CHCH 3，C（CH 3）2，O，S，NR 1或 SO2 + L，R1为H或烷基，m为0-10，（c）有效量的自由基引发剂。

26. 发明授权

US4764239A Substituted saccharin compounds and curable compositions containing same 失效
标题翻译：取代的糖精化合物和含有它们的可固化组合物
公开(公告)号：US4764239A
公开(公告)日：1988-08-16
申请号：US899377
申请日：1986-08-04
申请人： Anthony F. Jacobine , David M. Glaser
发明人： Anthony F. Jacobine , David M. Glaser
IPC分类号： C07D275/06 , C08F290/06 , C09J4/00 , C09J5/02
CPC分类号： C07D275/06 , C08F290/068 , C09J4/00
摘要： A curable composition including a monomer having at least one curable acrylic functionality, an accelerator and optionally a free radical initiator, wherein the accelerator is a compound of the formula ##STR1## wherein R' is H or alkyl; when R' is H, R is substituted or unsubstituted cyclohexyl, alkenylamino, or C.sub.3 -C.sub.10 branched alkyl; andwhen R' is alkyl, R is aralkyl.Such compositions are useful as fixturing (e.g., threadlocking) compositions, and overcome the problems of poor solubility in organic non-polar media and temperature constraints associated with the use of saccharin per se as an accelerator in such compositions.Also disclosed is a corresponding method of polymerizing compositions containing acrylic-functional compounds, and a method of making the substituted saccharin compounds from the corresponding substituted benzene sulfonamide.Alkenylamido-substituted saccharin compounds and alkyl, aralkyl-disubstituted saccharin compounds are specifically disclosed.
摘要翻译：一种可固化组合物，其包含具有至少一种可固化丙烯酸官能团的单体，促进剂和任选的自由基引发剂，其中促进剂是下式的化合物，其中R'是H或烷基; 当R'是H时，R是取代或未取代的环己基，链烯基氨基或C 3 -C 10支链烷基; 当R'为烷基时，R为芳烷基。这样的组合物可用作固定（例如，螺纹锁定）组合物，并且克服了在有机非极性介质中溶解度差的问题以及与在此类组合物中使用糖精本身作为促进剂相关的温度约束的问题。还公开了包含丙烯酸官能化合物的聚合组合物的相应方法，以及由相应的取代苯磺酰胺制备取代的糖精化合物的方法。烷基酰氨基取代的糖精化合物和烷基芳烷基二取代的糖精化合物被具体公开。

27. 发明授权

US5558937A Optical fiber primary coatings and fibers coated therewith 失效
公开(公告)号：US5558937A
公开(公告)日：1996-09-24
申请号：US433722
申请日：1995-05-03
申请人： John G. Woods , Margaret A. Rakas , Anthony F. Jacobine , Louis M. Alberino , Philip L. Kropp , Donna M. Sutkaitis , David M. Glaser , Steven T. Nakos
发明人： John G. Woods , Margaret A. Rakas , Anthony F. Jacobine , Louis M. Alberino , Philip L. Kropp , Donna M. Sutkaitis , David M. Glaser , Steven T. Nakos
IPC分类号： B29C67/00 , C03C25/10 , C07D263/42 , C08F2/50 , C08F6/02 , C08F8/34 , C08F8/42 , C08G65/332 , C08G73/02 , C08G75/04 , C09D4/00 , G02B6/44 , G03F7/00 , G03F7/027 , G02B6/00 , C08G75/12 , D02G3/00
CPC分类号： G02B6/443 , B29C67/0066 , C03C25/106 , C07D263/42 , C08F6/02 , C08G65/332 , C08G73/028 , C08G75/045 , C09D4/00 , G03F7/0037 , G03F7/0275 , Y10T428/2938
摘要： A curable thiol-ene composition specially adapted for use as a primary coating on optical fibers comprises a polythiol and a compound having a plurality of norbornene groups thereon, are characterized in that one of either the compound having the plurality of norbornene groups or the polythiol has a backbone of a poly(tetramethylene oxide), or is an oligomer thereof, and the poly(tetramethylene oxide) has a molecular weight of between 250 and 5,000. The formulations are relatively low viscosity liquids at practical application temperatures and cure substantially completely with very low irradiation fluence. The formulations cure in ambient air. There is no need to exclude oxygen or to control humidity. The formulations of the invention can be cured using low intensity UV lamps which do not generate significant amounts of heat. The cured products have excellent low temperature flexibility, good humidity and water absorbtion resistance and good thermal oxidative stability. The formulations may be applied to optical fibers using conventional techniques and cured with UV-vis or EB irradiation.

28. 发明授权

US5459175A Optical fiber primary coatings and fibers coated therewith 失效
标题翻译：光纤初级涂层和涂覆的纤维
公开(公告)号：US5459175A
公开(公告)日：1995-10-17
申请号：US80748
申请日：1993-06-22
申请人： John G. Woods , Margaret A. Rakas , Anthony F. Jacobine , Louis M. Alberino , Philip L. Kropp , Donna M. Sutkaitis , David M. Glaser , Steven T. Nakos
发明人： John G. Woods , Margaret A. Rakas , Anthony F. Jacobine , Louis M. Alberino , Philip L. Kropp , Donna M. Sutkaitis , David M. Glaser , Steven T. Nakos
IPC分类号： B29C67/00 , C03C25/10 , C07D263/42 , C08F2/50 , C08F6/02 , C08F8/34 , C08F8/42 , C08G65/332 , C08G73/02 , C08G75/04 , C09D4/00 , G02B6/44 , G03F7/00 , G03F7/027
CPC分类号： G02B6/443 , B29C67/0066 , C03C25/106 , C07D263/42 , C08F6/02 , C08G65/332 , C08G73/028 , C08G75/045 , C09D4/00 , G03F7/0037 , G03F7/0275 , Y10T428/2938
摘要： A curable thiol-ene composition specially adapted for use as a primary coating on optical fibers comprises a polythiol and a compound having a plurality of norbornene groups thereon, are characterized in that one of either the compound having the plurality of norbornene groups or the polythiol has a backbone of a poly(tetramethylene oxide), or is an oligomer thereof, and the poly(tetramethylene oxide) has a molecular weight of between 250 and 5,000. The formulations are relatively low viscosity liquids at practical application temperatures and cure substantially completely with very low irradiation fluence. The formulations cure in ambient air. There is no need to exclude oxygen or to control humidity. The formulations of the invention can be cured using low intensity UV lamps which do not generate significant amounts of heat. The cured products have excellent low temperature flexibility, good humidity and water absorbtion resistance and good thermal oxidative stability. The formulations may be applied to optical fibers using conventional techniques and cured with UV-vis or EB irradiation.
摘要翻译：特别适用于光纤上的初级涂层的可固化硫醇烯组合物包括多硫醇和其上具有多个降冰片烯基团的化合物，其特征在于具有多个降冰片烯基团的化合物或多硫醇中的一种具有聚（四氢呋喃）氧化物的骨架或其低聚物，并且聚（四氢呋喃）的分子量为250-5,000。制剂在实际应用温度下是相对低粘度的液体，并且以非常低的照射能量密度完全固化。配方在环境空气中固化。不需要排除氧气或控制湿度。本发明的配方可以使用不产生大量热量的低强度UV灯来固化。固化产物具有优异的低温柔韧性，良好的湿度和吸水性，良好的热氧化稳定性。可以使用常规技术将制剂施用于光纤并用UV-vis或EB辐照固化。

29. 发明授权

US5167882A Stereolithography method 失效
标题翻译：立体图法
公开(公告)号：US5167882A
公开(公告)日：1992-12-01
申请号：US651271
申请日：1991-02-05
申请人： Anthony F. Jacobine , Margaret A. Rakas , David M. Glaser
发明人： Anthony F. Jacobine , Margaret A. Rakas , David M. Glaser
IPC分类号： B29C67/00 , C08G75/04 , G03F7/00 , G03F7/027
CPC分类号： B29C67/0055 , C08G75/045 , G03F7/0037 , G03F7/0275 , Y10S522/91
摘要： An improved stereolithography method for building a three-dimensional article including the steps of patternwise curing successive layers of a bath of curable liquid resin formulation until the article has been completely built up, removing the article from the liquid resin bath and then post-curing the article, wherein the liquid resin is a "thiol/nene" formulation including:(a) a first compound having a plurality of norbornene groups thereon;(b) a second compound having a plurality of thiol groups therein; and(c) a free radical photoinitiator,the total functionality of the formulation being greater than 4.

30. 发明授权

US4622348A Chlorosulfonyl isocyanate derivatives as anaerobic accelerators 失效
标题翻译：氯磺酰基异氰酸酯衍生物作为厌氧促进剂
公开(公告)号：US4622348A
公开(公告)日：1986-11-11
申请号：US675387
申请日：1984-11-27
申请人： Anthony F. Jacobine , David M. Glaser
发明人： Anthony F. Jacobine , David M. Glaser
IPC分类号： C08F20/10 , C08F20/00 , C09J4/00 , C09J4/02 , C08F4/00
CPC分类号： C09J4/00 , Y10S522/904
摘要： Products formed from chlorosulfonyl isocyanate either by sequentially reaction of a hydroxy functional compound followed by reaction of the sulfonyl chloride group with a primary or secondary amine, or by reaction of chlorosulfonyl isocyanate with an excess of primary or secondary amine, are cure accelerators for acrylic compositions. Depending on the choice of alcohol or amine, the accelerator may be functionalized so that it is bound or bindable to an organic or silicone polymer backbone or contains other desirable functionality such as peroxy, photosensitizer, or acrylic groups.
摘要翻译：由氯代磺酰基异氰酸酯形成的产物通过羟基官能化合物的顺序反应，随后磺酰氯基团与伯胺或仲胺的反应，或通过氯代磺酰基异氰酸酯与过量的伯胺或仲胺的反应，形成丙烯酸组合物的固化促进剂。取决于醇或胺的选择，促进剂可以官能化，使其与有机或有机硅聚合物主链结合或结合，或含有其它所需官能团，如过氧化物，光敏剂或丙烯酸基团。

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