US009249251B2  (IO)  Patent No.:  US 9,249,251 B2  Feb.2,2016  (45)  Date of Patent:  c12)  United States Patent  Viswanathan et al.  (54)  COMPOSITIONS AND METHODS TO  PRODUCE  TRIAZINE-ARYLHYDROXY-ALDEHYDE  CONDENSATES WITH IMPROVED  SOLUBILITY  (75)  Inventors:  Ganapathy S. Viswanathan,  Louisville,  KY (US);  Raman C. Subrayan,  Louisville, KY (US);  Vinay Malhotra,  Louisville, KY (US)  (73)  Assignee:  HEXION INC.,  Columbus, OH (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 278 days.  (21)  Appl. No.:  12/858,096  (22)  Filed:  Aug.17, 2010  (65)  Prior Publication Data  US 2012/0046424 Al  Feb.23,2012  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ..............  C0SG 14110  (2013.01);  C0SG 591623  (2013.01);  C0SG 59/68  (2013.01);  C0SL 61/34  (2013.01)  (58)  Field of Classification Search  CPC ....................................................... C08G 14/10  USPC .......................................................... 525/523  See application file for complete search history.  C08G14/10  C0SG 73106  C0SL 61/00  C0SL 61/06  C0SL 63/00  C0SL 61/34  C08G59/62  C08G59/68  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (56)  References Cited  U.S. PATENT DOCUMENTS  3,293,212  A  12/1966 Power et al.  3,321,551 A  5/1967 Knutsson  3,364,167 A  1/1968 Imai et  al.  3,867,346  A  2/1975 Vargiu et al.  4,268,683  A  *  5/1981 Gurgiolo ......................... 560/24  5,034,527  A  7/1991 Brown eta!.  5,910,521  A  *  6/1999 Johnson et al. ............... 523/145  5,952,447  A  9/1999 Ikeda  5,955,184  A  9/1999 Honda et al.  6,239,248 Bl  5/2001 Gerber  6,392,003 Bl  5/2002 Kiuchi et al.  6,500,545 Bl  12/2002 Ambrose et al.  6,515,047 B2  2/2003 Fukuzawa et al.  6,558,797 Bl  *  5/2003 Arata et al . ................... 428/418  6,605,354 Bl  7,411,013 B2  *  2002/0058735 Al  2003/0148109 Al  2003/0224176 Al  2005/0003202 Al  2008/0241578 Al  *  2009/0054614 Al  8/2003 Gerber  8/2008 Harashina et al. ............ 524/117  5/2002 Galbo et al.  8/2003 Timberlake et al.  12/2003 Gerber  1/2005 Gerber  10/2008 Lin et al. ....................... 428/626  2/2009 Eguchi et al.  FOREIGN PATENT DOCUMENTS  CN  CN  EP  EP  JP  JP  JP  JP  JP  JP  JP  WO  WO  WO  1266859  1803873  0877040  0913413  H03243613  11279247  11279248  2001139666  2001164256  2004292791  2006077154  WO0009579  WO0025998  WO0194435  9/2000  7/2006  11/1998  5/1999  10/1991  10/1999  10/1999  5/2001  6/2001  10/2004  3/2006  2/2000  5/2000  12/2001  OTHER PUBLICATIONS  Shieh, J.-Y. and Wang, C.-S., Synthesis of Novel Flame Retardant  Epoxy Hardeners and Properties of Cured Products, Polymer., 2001,  pp. 7617-7625, No. 52, Elsevier Science Ltd.  Subrayan, Ramachandran et al., Condensation of Substituted  Phenols with Hexakis(methoxymethyl) melamine ... Chem. Mater.,  1998, pp. 3506-3512, vol. 10, No. 11, American Chemical Society.  Braun D. et al., "Gemeinsame Kondensation von Phenol, Melamin,  und  Formaldehyd.  I.  Modellreaktionen",  Angewandte  Makromolekulare Chemie., 1982, pp. 141-159, vol. 108, No. 1,  WileyVCH, Weinheim, D.E.  Maciejewski, M. et al., "Highly Branched Melamine-Phenolic  Novolaks", Polymer Bulletin, 2001, pp. 251-259, vol. 48, No. 3,  Springer, Heidelberg, DE.  * cited by examiner  Primary Examiner  - David Karst  Compositions and methods for forming condensates and  resin compositions are provided. In one embodiment, a con› densate is formed from a reaction mixture including a triazine  monomer, an arylhydroxy monomer, an aldehyde monomer  and an acid catalyst having a pKa value of greater than 3.8.  The condensates contain up to 28 wt. % of nitrogen and have  a melt viscosity of 3,000 cps or less at 175°  C. The conden› sates may have a solubility of at least 80 wt.  % solids dis› solved in an organic solvent for 120 hours or greater. Also  disclosed are methods for the manufacture of the condensate  as well as the condensate’s use in fire-retardant epoxy resin  compositions suitable for the manufacture of laminates for  electronic applications. There is also disclosed a glycidylated  triazine-arylhydroxy-aldehyde condensate of this invention.  (57)  ABSTRACT  24 Claims, No Drawings 