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(12) United States Patent (10) Patent No.: US 6,271,330 B1 Letchford Et Al USOO627133OB1 (12) United States Patent (10) Patent No.: US 6,271,330 B1 Letchford et al. (45) Date of Patent: Aug. 7, 2001 (54) FUNCTIONALIZED SILICONE POLYMERS OTHER PUBLICATIONS AND PROCESSES FOR MAKING THE SAME Lai et al., “Synthesis and Characterization of (75) Inventors: Robert James Letchford, Cherryville; C,0)-Bis-(4-hydroxybutyl) Polydimethylsiloxanes,” Jour James Anthony Schwindeman, nal of Polymer Science. Part A. Polymer Chemistry, vol. 33, Lincolnton, both of NC (US); Roderic 1773–1782 (1995). Paul Quirk, Akron, OH (US) Riffle, et al., “Elastomeric Polysiloxane Modifiers for Epoxy Networks,” Epoxy Resin Chemistry II, American Chemical (73) Assignee: FMC Corporation, Philadelphia, PA Society, 1983, pp. 21-54. (US) Wilczek et al., “Preparation and Characterization of Narrow Molecular Mass Distribution Polydimethylsiloxanes, Pol (*) Notice: Subject to any disclaimer, the term of this ish Journal of Chemistry, 55, 2419–2428 (1981). patent is extended or adjusted under 35 McGarth, et al., “An Overview of the Polymerization of U.S.C. 154(b) by 0 days. Cyclosiloxanes.” Initiation of Polymerization, American Chemical Society, 1983, pp. 145-172. (21) Appl. No.: 09/373,211 Yilgör et al., “Polysiloxane Containing Copolymers: A Sur vey of Recent Developments.” Advances in Polymer Sci (22) Filed: Aug. 12, 1999 ence, 86, 1 (1988). Yu et al., “Anionic polymerization and copolymerization of Related U.S. Application Data cyclosiloxanes initiated by trimethylsilylmethyllithium”, (62) Division of application No. 09/082,072, filed on May 20, Polymer Bulletin, 32, 35-40 (1994). 1998, now Pat. No. 6,031,060. Frye et al., “Reactions of Organolithium Reagents with (60) Provisional application No. 60/047,435, filed on May 22, Siloxane Substrates.” The Journal of Organic Chemistry, 1997. vol. 35, No. 5, pp. 1308–1314, (May, 1970). (51) Int. Cl." ................................................. C08G 77/06 Primary Examiner Robert Dawson (52) U.S. Cl. ................................. 528/14; 528/10; 528/21; Assistant Examiner Jeffrey B. Robertson 528/23: 528/30; 528/37; 528/38; 556/437 (74) Attorney, Agent, or Firm-Alston & Bird LLP (58) Field of Search .................................. 528/10, 14, 21, 528/23, 30, 37,38; 556/437 (57) ABSTRACT (56) References Cited Terminally functionalized Silicone polymers prepared using protected functionalized initiators and processes for prepar U.S. PATENT DOCUMENTS ing the same. The Silicone polymers includes protected, 5,296,574 3/1994 HOXmeier. functionalized Silicone polymers, Such as mono-functional, 5,486,635 1/1996 Okawa. homotelechelic, heterotelechelic, macromonomer, and radial 5,561,210 10/1996 Roy. polymers. The protected functionalized polymers can be 5,618,903 4/1997 Hoxmeier et al. optionally deprotected to afford functionalized Silicone polymers. FOREIGN PATENT DOCUMENTS 1289 526 9/1972 (GB). 13 Claims, No Drawings US 6,271,330 B1 1 2 FUNCTIONALIZED SILICONE POLYMERS protected homotelechelic polymers of formula (III): AND PROCESSES FOR MAKING THE SAME CROSS-REFERENCE TO RELATED in which each - T -(A-R7RR), as defined below is the APPLICATIONS 5 same; protected heterotelechelic polymers of formula (III): This application is a divisional of application Ser. No. 09/082,072, filed May 20, 1998, now U.S. Pat. No. 6,031, 060, and is related to provisional application Ser. No. 60/047,435, filed May 22, 1997, and claims the benefit of its in which each - T -(A-RRR), as defined below dif filing date under 35 USC S 119(e). fers; protected heterotelechelic polymers of formula (III"): FIELD OF THE INVENTION This invention relates to novel protected functionalized in which - T -(A-RRR), and FG differ; and protected Silicone polymers, their optionally deprotected analogues, 15 radial polymers of the formula (IV): and to processes for preparing Silicone polymers. BACKGROUND OF THE INVENTION in which each -T (A-R7RR) may be the same or Silicone polymers have many unique properties, Such as different. wide Service temperature range, low Viscosity change verSuS In each of Formula (I), (II), (II), (III), (III), (III"), and temperature; low flammability; shear Stability; chemical (IV) above: inertness; oxidative stability; UV stability; low toxicity; and Q is an unsaturated hydrocarbyl group derived by incor the like. These properties have facilitated their adoption as poration of one or more conjugated die ne dielectric, hydraulic, heat transfer, power transmission and hydrocarbons, one or more alkenylsubstituted aromatic damping fluids. Silicone polymers have also found applica 25 compounds, or mixtures of one or more dienes with one tion as additives incorporated into plastics and rubbers as or more alkenylsubstituted aromatic compounds into proceSS and release aids, into coatings for flow and level the M-Z linkage; control and into proceSS Streams as antifoams. Other unique n is an integer from 0 to 5; properties have led to their introduction in acoustical appli Z is a branched or Straight chain hydrocarbon connecting cations Such as ultraSonic Sensor and Sonar buoys. This group which contains 3–25 carbon atoms, optionally proliferation of applications has engendered many improve Substituted with aryl or substituted aryl; ments and refinements of Silicone polymers. T is Selected from the group consisting of OXygen, Sulfur, Anionic polymerization of cycloSiloxanes, particularly and nitrogen groups, and mixtures thereof; hexamethylcyclotrisiloxane (D) and octamethyltetrasilox 35 (A-R'R'R''), is a protecting group in which A is an ane (D), has been reported previously. It is known that D. element selected from Group IVa of the Periodic Table polymerization does not occur in hydrocarbon Solvents. C. of the Elements; R7, R, and Rare each independently L. Frye, R. M. Salinger, F. W. Fearon, J. M. Klosowski and Selected from the group consisting of hydrogen, alkyl, T. deYoung, J. Org. Chem., 35, 1308 (1970). Although the Substituted alkyl, aryl, Substituted aryl, cycloalkyl, and anionic species was formed (Bu-Si(CH))-O-Li'), it 40 did not polymerize. Addition of a polar promoter, Such as Substituted cycloalkyl, and m is 1 when T is oxygen or THF, diglyme, or DME then stimulated the polymerization. Sulfur, and 2 when T is nitrogen; J. M. Yu, D. Teyssie, R. B. Khalife and S. Boileau, Polymer v is an integer from 2 to 100,000; bulletin, 32, 35-40 (1994). The resultant polymer anion R" and Rare each independently selected from the group PDMS-O-Li' can then be protonated to afford PDMS 45 consisting of hydrogen, alkyl, Substituted alkyl, OH, capped with a silicon halide (R'R'R-Si-X) to afford alkenyl, Substituted alkenyl, aryl, and Substituted aryl; PDMS-O-SiRR'R'', or coupled with suitable coupling R. R', and Rare each independently selected from the agents (SiCl, MeSiCl, HSiCOMe)) to afford (PDMS), group consisting of hydrogen, alkyl, Substituted alkyl, wherein n is the number of coupling agent functionalities. In fluorinated alkyl, alkyl containing an acetal Spite of considerable Synthetic efforts, however, there are 50 functionality, alkenyl, Substituted alkenyl, aryl, and few good ways to affix functionality to the termini of the Substituted aryl; Silicone polymers. R, R", and Rare each independently selected from the group consisting of hydrogen, alkyl, Substituted alkyl, SUMMARY OF THE INVENTION fluorinated alkyl, alkyl containing an acetal The present invention provides novel protected function 55 functionality, alkenyl, Substituted alkenyl, aryl, Substi alized Silicone polymers. Exemplary protected functional tuted aryl, and free radically polymerizable groups, ized Silicone polymers of the invention include protected with the proviso that at least one R, R", and R is a functionalized polymers of formula (I): free radically polymerizable group; FG is a protected or non-protected functional group; 60 L is a residue of a difunctional linking agent, Such as a protected functionalized polymers of formula (II): SiMe residue derived from the difunctional linking agent SiMeCl; (RVRR-A), T-Z-Q-(R'R'Si-O)-SiRRR (II): L' is a residue of a multifunctional linking agent, Such as 65 a Si residue derived from the multifunctional linking protected functionalized macromonomers of formula (II): agent SiCl, and Z is an integer from 3 to 20. US 6,271,330 B1 3 4 The present invention also provides functionalized sili ization reactions, or reaction with methacroyl chloride to cone polymers as described above in which at least one afford a macromonomer. The remaining protecting groups protecting group -(A-RRR), has been removed to can then be removed, and then these functional groups can liberate the protected functionality T (oxygen, nitrogen, or then participate in further copolymerization reactions. Sulftir). The functional groups can then optionally partici pate in various copolymerization reactions by reaction of the DETAILED DESCRIPTION OF THE functional groups on the ends of the polymer arms with INVENTION Selected difunctional or polyfunctional comonomers as described in more detail below to provide a Silicone polymer The Silicone polymers of the present invention include the having polymer Segments. polymers of the following formulas: The novel polymers of the invention can be optionally protected functionalized polymers of formula (I): hydrogenated to afford other novel polymers. The protecting groups can be removed either prior to or following hydro genation. protected functionalized polymers of formula (II): The polymers of the invention can be prepared by anionic 15 polymerization of one or more Suitable
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