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United States Patent (19) 11 Patent Number: 5,677,388

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United States Patent (19) 11 Patent Number: 5,677,388 US005677388A UnitedO States Patent (19) 11 Patent Number: 5,677,388 Koster et al. 45 Date of Patent: Oct. 14, 1997 54 DIFUNCTIONAL LIVING FREE RADICAL 5,401,804 3/1995 Georges et al. POLYMERIZATION INITIATORS 5,412,047 5/1995 Georges et al. 5,498,679 3/1996 Moffat et al. ........................... 526/204 75 Inventors: Robert A. Koster; Duane B. Priddy; HER rene Li, all of Midland, Mich. OT PUBLICATIONS 8 J. Org. Chem. (1992) 57(3), 982-8. 73) Assignee: The Dow Chemical Company, J. Am. Chem. Soc. 1994, 116, 11185-11186 (Craig H. Midland, Mich. Hawker). Polymer Preprints, Synthesis, Characterization, and Evalu (21) Appl. No.: 731,216 ation of Initiators for Living Free Radical Polymerization: 22 Filed: Oct. 8, 1996 Synthesis of Polystyrene w/Controlled Structure vol.36, No. 1, Apr. 1995. Related U.S. Application Data city in Australia, Jan.-Feb. 1987, p. 32 (Ezio Riz 62) Division of Ser. No. 533,799, Sep. 26, 1995. Macromolecules 1995, 28, 4391-4398, Veregin, et al. 6 J. Org. Chem. vol. 40, No. 23, 1975, pp. 3448-3450. 51) int. Cl. ............................ C08F 293/00; CO8F 4/04; Makromol. Chem. Rapid Commun. 3, 533-536 (1982), C08F 4/34 Moad et al. 52 U.S. Cl. .......................... 525/314; 525/273; 525/267 Angew. Chem. Int. Ed. Engl. 1995, 34, No. 13/14, pp. 58 Field of Search ................................... 525/273,314, 1456-1459, (Hawker). 525/267 Primary Examiner-Joseph L. Schofer 56 References Cited Assistant Examiner Wu C. Cheng U.S. PATENT DOCUMENTS 57 ABSTRACT 4,581,429 4/1986 Solomon et al. A living free-radical polymerization process for preparing 5,051,511 9/1991 Seltzer et al.. polymers from vinyl aromatic monomers comprising poly 5,140,081 8/1992 Seltzer et al., merizing the vinyl aromatic monomer in the presence of a 5,145,893 9/1992 Galbo et al. difunctional nitroxyl initiator 5,204,422 4/1993 Seltzer et al.. y 5,312,871 5/1994 Mardare et al.. 5,322,912 6/1994 Georges et al. 7 Claims, No Drawings 5,677.388 1 2 DFUNCTIONAL LIVING FREE RADICAL monomers may also be combined with other copolymeriz POLYMERIZATION INITIATORS able monomers. Examples of such monomers include but are not limited to acrylic monomers such as acrylonitrile, This is a divisional of application Ser. No. 08/533,799 methacrylonitrile, methacrylic acid, methyl methacrylate, filed Sep. 26, 1995. butyl acrylate, acrylic acid, and methyl acrylate, maleic anhydride, maleimide, and phenylmaleimide. In addition, BACKGROUND OF THE INVENTION the polymerization may be conducted in the presence of predissolved elastomer to prepare impact modified, or This invention relates to a living free radical polymeriza grafted rubber containing products, examples of which are tion process. described in U.S. Pat. Nos. 3,123,655, 3,346.520,3639,522, A process for producing low polydispersity polymers by 10 and 4,409,369. free-radical chemistry using a living polymerization is dis Difunctional nitroxyl initiators useful in the process of the present invention, include any dinitroxyl compound which closed in Macromolecules 1993, 26, 2987, by Georges etal. will initiate living free radical polymerization, wherein However, this process utilizes monofunctional initiators and polymer chain growth occurs between the two nitroxyl reports reaction times of 21 hours or more. 15 groups, and produce a telechelic polymer. A telechelic Another method of preparing low polydispersity vinyl polymer is a polymer having two functionalized chain-ends aromatic polymers having accurate molecular weight con as described in "Telechelic Polymers". Encycopedia of Poly trol and block copolymer formation, giving rise to well mer Science and Engineering, 1989, Vol. 16, pages defined end groups, is disclosed in J. Am. Chem. Soc. 1994, 494-532. Preferably, the difunctional nitroxyl initiators are 116, 11185-11186, by Hawker using a monofunctional 20 of the formula: nitroxyl initiator. However, long reaction times, e.g. 72 hours, are again required to reach a desirable conversion. It would be highly desirable to utilize the control of the living free radical polymerization to produce high molecular weight vinyl aromatic polymers within shorter reaction 25 times and produce block copolymers in a more efficient wherein R' is a linking group, R and Rare each indepen 2. dently H, alkyl, cycloalkyl, an activating group, or together form an alkyl bridging group, R and Rs are each indepen SUMMARY OF THE INVENTION dently alkyl, aryl, or together form an optionally alkyl 30 substituted ring wherein the ring contains from about 4 to 10 The present invention is a living free-radical polymeriza carbon atoms such as a 2,26,6-tetramethyl-1-piperidinyl tion process for preparing polymers from vinyl aromatic group, with the proviso that each C is attached to at least one monomers comprising polymerizing the vinyl aromatic activating group. monomer in the presence of a difunctional nitroxyl initiator. Any alkyl group is defined as a group containing from 1 A second aspect of the present invention is a difunctional 35 to 6 carbon atoms, and any aryl group as containing 1-3 nitroxyl initiator which is a telechelic polymer macroinitia aromatic rings. An activating group is defined as a group tor comprising a polymer having nitroxyl functionalized wherein the point of attachment must be a carbon atom chain-ends. which is unsaturated or aromatic, such as an alkenyl, cyano, These initiators are especially useful in a process for carboxyl or aryl group. An alkyl bridging group is defined as preparing triblock copolymers such as polystyrene a divalent alkyl group which is attached to both C atoms. polyacrylate-polystyrene copolymers which are useful as R" can be any linking group, as long as C is attached to adhesives and as compatibilizers for polymer blends, and at least one activating group. It may be saturated or polybutadiene triblock copolymers such as styrene/ unsaturated, and contain non-carbon atoms, including but acrylonitrile-polybutadiene-styrenefacrylonitrile and not limited to sulfur, nitrogen and/or oxygen. Typical linking polystyrene-polybutadiene-polystyrene block copolymers, 45 groups include alkylene, cycloalkylene and phenylene which are especially useful as polymer toughening agents. groups. Alkylene is defined as a bivalent hydrocarbon group, cycloalkylene as a bivalent cyclic hydrocarbon group, and DETALED DESCRIPTION arylene as a bivalent aryl group. Suitable monomers used in the process of the present In some instances it is advantageous for the linking group invention include vinyl aromatic monomers typically rep 50 to contain a functional group capable of initiating normal resented by the formula: free radical polymerization at a temperature below the nitroxyl activation temperature. The nitroxyl activation tem R perature is defined as a temperature at which living free radical polymerization occurs at areasonable rate. Typically, Ar-CECH 55 this occurs attemperatures above about 120° C., preferably between about 120° and 170° C. Such groups include azo, wherein R is hydrogen or methyl, Ar an aromatic ring disulfide or peroxide functionalities. structure having from 1 to 3 aromatic rings with or without In other cases it is advantageous for the linking group to alkyl, halo, or haloalkyl substitution, wherein any alkyl contain a C=C bond capable of undergoing addition group contains 1 to 6 carbon atoms and haloalkyl refers to fragmentation chain transfer. a halo substituted alkyl group. Preferably, Ar is phenyl or In yet other instances, it is advantageous for the linking alkylphenyl with phenyl being most preferred. Typical vinyl group to contain both a functional group capable of initiating aromatic monomers which can be used include: styrene, normal free radical polymerization at a temperature below alpha-methylstyrene, allisomers of vinyl toluene, especially the nitroxyl activation temperature and a C=C bond capable para-vinyltoluene, all isomers of ethyl styrene, propyl 65 of undergoing addition-fragmentation chain transfer. styrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene Preferably, R is arylene and R2 and Ra are not both H, and the like, and mixtures thereof. The vinyl aromatic more preferably R is arylene, R2 is methyl and R is H, and 5,677,388 3 4 most preferably R is arylene, R is methyl, R is H and R. -continued and Rs together form a 2.26.6-tetramethyl-1-piperidinyl group. o In another embodiment of the present invention, the / \ difunctional nitroxyl initiator is a telechelic polymer CH- N-C-S macroinitiator, such as a polybutadiene, polyacrylate or O M ? 2. polycarbonate having nitroxyl functionalized chain-ends. N Examples of difunctional nitroxyl initiators include but are not limited to: C (6) Azo initiators - Peroxide Initiators O N -( y-oCN-- O O CNI 2 N - O C (1) O (7) ^^++ JCl 30 r (2) Disulfide initiators 35 -- (8) 40 45 (9) -N-soO CN (10) st 55 (4) Addition-Fragmentation Chain Transfer Agents O o Ph PN-r O--- s^ O O N N O Of 65 (11) (5) 5,677,388 5 6 -continued -continued O N N 5 O O OCH O HOC r oN 2. N HO 10 COH C (17) (12) 15 O Ph N r oS-ACO O O O N --s-s orn- Ph O O Of C. N (13) 25 JOk O N Cl 30 CN 2. (19) 35 O (14) OS-N-S O COMe 2 Other Dinitroxides (20) f 45 r -N r" D. 50 (15) (21) 55 D. r (16) 65 5,677,388 7 8 -continued -continued O NOS-N- orn Ph CN O O CH2 O PN-ro l o1N1-1NoN l Ph 10 t (26) P Ph t t NO ON ) (22) (27) O N 25 N o O Of O O-CH C OH 2. -- O (28) (23) (CH2)2 35 O O CO2H C C. 40 (29) These difunctional nitroxyl initiators can be prepared from the desired precursors, such as C-R-C containing -O- 45 compounds, by forming radicals in the presence of a nitroxyl containing compound which traps the radical intermediates -- (24) as they form.
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