US00757617OB2 (12) United States Patent (10) Patent No.: US 7,576,170 B2 Perry et al. (45) Date of Patent: Aug. 18, 2009 (54) CYCLIC SILOXANE COMPOSITIONS FOR 6,046,156 A 4/2000 Perry THE RELEASE OF ACTIVE INGREDIENTS 6,054,547 A 4/2000 Perry et al. 6,063,365 A 5, 2000 Schefer et al. (75) Inventors: Robert J. Perry, Niskayuna, NY (US); 6,075,111 A 6/2000 Perry et al. Mark D. Leatherman, Elmsford, NY 6,077.923 A 6/2000 Perry et al. (US); Shahid Murtuza, Albany, NY 6,083,901 A 7/2000 Perry et al. (US) 6,121,343 A 9/2000 Hongo et al. 6,143,309 A 11/2000 Legrow et al. (73) Assignee: Momentive Performance Materials, 6,153,578 A 11/2000 Perry Albany, NY (US) 6,200,949 B1 3/2001 Reijmer et al. 6,228,380 B1 5, 2001 LeGrow et al. (*) Notice: Subject to any disclaimer, the term of this 6,262,287 B1 7/2001 Anderson et al. patent is extended or adjusted under 35 6,267,977 B1 7/2001 LeGrow et al. U.S.C. 154(b) by 993 days. 6,309,715 B1 10/2001 Lindauer et al. 6,322,777 B1 1 1/2001 Perry et al. (21) Appl. No.: 10/742,415 6,325,274 B2 12/2001 Esumi et al. 6,325,859 B1 12/2001 De Roos et al. (22) Filed: Dec. 19, 2003 6,435,423 B2 8/2002 Hurry et al. (65) Prior Publication Data 6,624,136 B2 9, 2003 Guerinet al. 2002/0156223 A1 10/2002 Boudjouket al. US 2005/O136O22 A1 Jun. 23, 2005 (51) Int. Cl. FOREIGN PATENT DOCUMENTS COSL 83/06 (2006.01) COSL 83/05 (2006.01) EP 106.124 A2 9, 1983 C08G 77/12 (2006.01) EP 106.124 B1 9, 1983 C08G 77/14 (2006.01) EP 273266 A2 12/1987 C08G 77/16 (2006.01) EP 273266 A3 12/1987 EP O334490 A2 2, 1989 (52) U.S. Cl. ............................. 528/37; 528/25; 528/29: EP O334490 A3 2, 1989 528/31:528/33 EP O334490 B1 2, 1989 (58) Field of Classification Search ....................... None EP 878497 A2 5, 1998 See application file for complete search history. EP 878497 A3 5, 1998 (56) References Cited EP O 878 497 A 11, 1998 EP O982 022 A 3, 2000 U.S. PATENT DOCUMENTS EP O982 O23 A 3, 2000 3,215,719 A 11, 1965 Allen et al. EP O998 911 A 5, 2000 3,271,305 A 9, 1966 Allen et al. 4,445,641 A 5, 1984 Baker et al. 4,500,725 A 2f1985 Yemoto et al. (Continued) 4,524,018 A 6, 1985 Yemoto et al. 4,908,208 A 3, 1990 Lee OTHER PUBLICATIONS 5,008, 115 A 4, 1991 Lee et al. 5,049,182 A 9, 1991 Scher et al. Daum, Jeremy et al: “Synthesis and characterization of novel 5,071,704 A 12/1991 Fischel-Ghodsian cyclosiloxanes and their self- and co-condensation with silanol-ter 5,130,171 A 7, 1992 Prud’Homme et al. minated polydimethylsiloxane' Polymer Reprints, vol. 45, No. 2, 5,139,864 A 8, 1992 Lindauer 2004, pp. 539-540, XP009048491.ISSN: 0032-3934, table 1. 5,160.494. A 1 1/1992 Krzysik et al. 5,176,903. A 1/1993 Goldberg et al. (Continued) 5,185,155 A 2f1993 Behan et al. Primary Examiner Michael J Feely 5,213,409 A 5, 1993 Fisher (74) Attorney, Agent, or Firm Kenneth S. Wheelock 5,234,689 A 8, 1993 Lindauer et al. 5,324.444 A 6/1994 Berry et al. (57) ABSTRACT 5,372,806 A 12/1994 Holloway 5,378.468 A 1/1995 Sufis et al. 5,387,411 A 2/1995 Abrutyn et al. Cyclic siloxanes that contain releasable active ingredients are 5,387,622 A 2f1995 Yamamoto described. The active ingredient can be an alcohol or enoliz 5.449,512 A 9, 1995 Simmons able carbonyl-containing compound Such as a ketone, alde 5.490,982 A 2f1996 Sicilliano hyde, or ester. The product siloxanes are useful in a variety of 5,500,223. A 3, 1996 Behan et al. personal and household care products where slow or con 5,525,555 A 6, 1996 Zank trolled release of active ingredient is desired. A preferred 5,525,588 A 6, 1996 Michetti embodiment utilizes substituents that when released as active 5,587,151 A 12/1996 Richard et al. 5,847,179 A 12/1998 LeGrow et al. ingredients are fragrant. 5,867,755 A 2, 1999 Sato 6,042,792 A 3, 2000 Shefer et al. 21 Claims, No Drawings US 7,576,170 B2 Page 2 FOREIGN PATENT DOCUMENTS trichlorophenylsilane and propyl and butyl alcohols'. EP 1178.107 A2 T 2000 XP00233 18909, Database accession No. 1988:75470, compounds EP 1178.107 A3 T 2000 under the registry Nos. 112671-14-4. 112671-15-5, 112671-21-3, EP 1116515 A2 12/2000 11261-22-4, 11267-28-0 & 112671-34-8 abstract—& Voprosky EP 1116515 A3 12/2000 Khimii I Khimicheskoi Tekhnologii, vol. 81, 1986, pp. 79-90, EP 1133929 A1 3, 2001 XPOO9048490 ISSN: 0321-4059. GB 971 309 A 9, 1964 Sprung M M et al: “The partial hydrolysis of GB 2041964. A 1, 1980 methyltrimethoxysilane” Journal of the American Chemical Society, GB 2042890 A 1, 1980 vol. 77, Aug. 5, 1955, pp. 4173-4 175, XP001206395, ISSN: 0002 JP 11047581 A 2, 1999 7863, Compounds II. JP 2002O2O783. A 1, 2002 WO WO9628497 A1 9, 1996 Okawara.<Rokuro et al: "Alkylalkoxypolysiloxanes. VI. Lower WO WO9815192 A1 4f1998 members of cyclic methyl- and ethylethoxypolsiloxanes' Bulletin of WO WOOO16643 A1 3, 2000 the Chemical Society of Japan, vol. 31, No. 1 Jan. 1958, pp. 22-25, WO WOOO16643 A5 3, 2000 XPO09048486, ISSN: 0009-2673, table IV. WO WOOO64497 A1 11 2000 Okawara, Rokuro et al: "Alkylalkoxypolysiloxanes. VII. Lower WO WOO1731.88 A1 10/2001 members of cyclic methyl- and ethylisopropoxypolsiloxanes' Bul WO WOO179303 A1 10/2001 letin of the Chemical Society of Japan, vol. 33, No. 5, May 1960, pp. WO WOO2O6585 A1 1, 2002 659-660, XPO09048487, ISSN: 0009-2673, table III. WO WOO24.1709 A1 5, 2002 WO WOO2O76514 A2 10, 2002 Andrianov, L. A. et al: "Organic phosphosilicon compounds of WO WOO2O76514 A3 10, 2002 sterecyclic structure', Bulletin of the Academy of Sciences of the WO WOO2O83620 A1 10, 2002 USSR, Division of Chemical Sciences, vol. 11, 1969, pp. 2300-2306, WO WOO3O32749 A1 4/2003 XPO09048488, iSSN: 0.568-5230, 7th and 8th entries in table 1. Crandall J K et al: "Siloxanes from the hydrolysis of OTHER PUBLICATIONS isopropyltrimethoxysilane' Jornal of Organometallic Chemistry, Database Caplus 'Online Chemical Abstracts Service.< Columbus, vol. 489, No. 1, Mar. 8, 1995, pp. 5-13, XP004024184, ISSN: 0022 Ohio, US; 1988, Kuz Menko, N. Ya. et al: “Etherification of 328X. Compounds 7, 8 and 13. US 7,576,170 B2 1. 2 CYCLIC SILOXANE COMPOSITIONS FOR lanes (U.S. Pat. No. 5,847, 179) and derivatization of silanes THE RELEASE OF ACTIVE INGREDIENTS with hydroxycarboxylic acid skin exfoliants to form (triorga nosilyl)alkoxycarboxylates (U.S. Pat. Nos. 6,143,309; 6,228. CROSS-REFERENCE TO RELATED 380; 6,267,977) have been described. Direct displacement of APPLICATIONS an alkoxy leaving group on a silicon atom by a fragrant alcohol was reported by Allen, et al. to give fragrant silicon Not Applicable esters or linear silicate esters (U.S. Pat. Nos. 3,215,719 and 3.271.305). Several others also reported similar alkoxy dis STATEMENT REGARDING FEDERALLY placement reaction to form linear fragrant siloxane polymers FUNDED RESEARCH or copolymers (GB 2,041,964; GB 2,042,890; EP 273266). 10 Reaction of an alcohol, aldehyde, ketone or lactone with a Not Applicable silyl hydride in the presence of a metal carboxylate salt and a reducing agent to form linear polymers and copolymers was FIELD OF THE INVENTION also reported (WO 96.28497). Other routes to fragrant sili cones using silyl hydrides were disclosed by Anderson, et al. The present invention relates to cyclic siloxanes, Suitable 15 (EP 878497, JP 10330382, U.S. Pat. No. 6,262,287) and for use in a variety of applications including personal care Perry, et al. (U.S. Pat. Nos. 6,046,156; 6,077,923; 6,153,578; formulations, perfumes, household products, detergents, 6,054,547; 6,075,111; 6,322,777; 6,083,901). In these pro rinse additives, automotive, textiles and molding materials, cesses, hydrosilylation chemistry was employed to join the wherein the cyclic siloxane has been chemically modified to active portion of the molecule to the silicone backbone. What release an active ingredient upon hydrolysis. The present is not taught or Suggested by the prior art is the formation and invention further relates to such molecules where the rate of use of active ingredient-functional cyclic siloxane composi active ingredient release is Sufficiently slow so that products tions for personal care, textile, laundry or plastics applica formulated with the modified cyclic siloxane exhibit the tions. Herein we disclose a new composition and method for desired effect for long periods of time. preparation of active ingredient functional cyclic siloxane articles from cyclic silyl hydrides. The method is the direct 25 reaction of an alcohol- or carbonyl-containing compound BACKGROUND OF THE INVENTION with the cyclic silyl hydride in the presence of a catalyst to The slow, Sustained release of an active ingredient is a generate the product and hydrogen gas byproduct.