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Chain-Transfer Agents for Emulsion Polymerization and Polymer Products Produced Therewith

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Chain-Transfer Agents for Emulsion Polymerization and Polymer Products Produced Therewith Europaisches Patentamt European Patent Office © Publication number; 0 199 316 Office europeen des brevets A2 © EUROPEAN PATENT APPLICATION © Application number: 86105429.4 © Int. CI.': C 08 F 20/12 C 08 F 2/38 ^ © Date of filing: 18.04.86 © Priority: 25.04.85 US 727155 © Applicant: PHILLIPS PETROLEUM COMPANY 5th and Keeler Bartles ville Oklahoma 74004(US) @ Date of publication of application: 29.10.86 Bulletin 86/44 @ Inventor: Bobsein, Rex Leo 200 N.E. Spruce ® Designated Contracting States: Bartiesvllle, OK 74006IUS) AT BE CH DE FR GB IT U LU NL SE © Inventor: Undstrom, Merlin Ray 4752 S.E. Frank Phillips Blvd. Bartiesvllle, OK 74006(US) © Representative: Dost, Wolfgang. Dr. rer. nat. Dipl.-Chem. et al. Patent- u. Rechtsanwitte Bardehle, Pagenberg. Dost, Artenburg Frohwftter & Partner Galileipiatz 1 D-8000Munchen80(DE) (5j) Chain-transfer agents for emulsion polymerization and polymer products produced therewith. In the emulsion polymerization of acrylic monomers, an improvement comprises the use of 3-mercaptopropionate esters as chain-transfer agents. Novel polymers are pro- duced by the inventive polymerization process. This invention relates to emulsion polymerization processes. In one aspect, this invention relates to chain-transfer agents for use in emulsion polymerization processes. In another aspect, this invention relates to acrylic polymers produced by emulsion polymerization. In yet another aspect this invention relates to the control of polymer molecular weight and molecular weight distribution in the emulsion polymerization processes. Background The emulsion polymerization process enjoys wide usage in the chemical industry. Many monomers can be polymerized using this technology. The method combines the economy and safety of an aqueous reaction medium with a rapid but readily controlled polymerization to provide high molecular weight polymers in excellent yield. Among the advantages of emulsion polymerization are reduced fire hazard, high reaction rate, production of high molecular weight polymer relative simplicity of the technology and production of low viscosity latexes. Shortcomings of emulsion polymerizations include the relative difficulty in separating the polymer product and contamination of the polymer product with residual emulsifier. Chain-transfer agents can be and are added to emulsion polymerization systems in order to improve final polymer properties. Chain-transfer agents are generally used in free radical polymerizations and function as molecular weight modifiers. The chain-transfer agent reacts with a growing polymer chain to form a "dead" polymer with the concurrent formation of a new center for polymer growth. The chain transfer mechanism for mercaptan containing chain-transfer agents can be depicted as follows: Among those polymer properties which it is desirable to control are polymer molecular weight distribution, freeze-thaw stability of the latex and polymer particle size. A narrow molecular weight distribution refers to a more nearly homogeneous polymer sample than a similar polymer blend having a broad molecular weight distribution. For many applications, polymers having a narrow molecular weight distribution is desirable. Freeze-thaw stability refers to the ability of a latex to remain as an emulsion even when exposed to heat-cool temperature cycles. Since emulsion latexes produced from acrylic monomers are susceptible to breakdown of the emulsion when exposed to temperature extremes over a period of time, emulsion latexes which are stable to exposure to freeze-thaw conditions are desirable in that breakdown of the emulsion with resultant settling of the polymer would be avoided. For certain applications, such as for example in coatings and adhesives, a polymer latex having a relatively uniform particle size would be desirable. It is generally observed, however, that acrylic polymers produced by emulsion polymerization have a rather broad particle size distribution, and thus are not well suited for the production of homogeneous coatings or the like. It is a continuing goal of those in the emulsion polymerization art to discover new chain-transfer agents which are effective for molecular weight modification and which provide polymer products with improved physical properties. Objects of the Invention An object of this invention, therefore, is a process for the control of molecular weight and molecular weight distribution of acrylic polymers produced by emulsion polymerization processes. Another object of this invention is novel acrylic polymers having improved physical properties. These and other objects of the invention will become apparent from the disclosure and claims provided herein. Statement of the Invention In accordance with the present invention, we have discovered that at least one compound selected from the group consisting of 3-mercaptopropionate esters, 6-mercaptomethyl-2-methyl-2-octanol, and 2-phenyl-1-mercapto-2-ethanol are effective chain-transfer agents in emulsion polymerization of acrylic monomers. By the practice of the present invention, acrylic polymers having reduced molecular weights as well as narrow molecular weight distributions are obtained. Additional beneficial physical properties of the novel polymers produced in accordance with the present invention will be detailed in the discussion which follows. Detail Description of the Invention In accordance with the present invention, an emulsion polymerization process is provided comprising polymerizing at least one acrylic monomer in aqueous medium under polymerization conditions in the presence of a water soluble free-radical initiator, an emulsifier and at least one compound selected from the group consisting of 3-mercaptopropionate esters, 6-mercaptomethyl-2-methyl-2-octanol, and 2-phenyl-l-mercapto-2-ethanol as chain-transfer agent. In accordance with another embodiment of the present invention, novel compositions are provided comprising a polymer of at least one acrylic monomer, wherein the polymer has a molecular weight in the range of 500 to 100,000, and a heterogeneity index not exceeding about 3.0; preferably the heterogeneity index will not exceed about 2.0; and most preferably the heterogeneity index will not exceed about 1.7. In addition, at least a portion of the individual molecules of the polymer are terminated by the radical: wherein R is a carbon containing radical having 1-20 carbon atoms. As employed herein, the term "carbon containing radicals" is intended to include carbon radicals containing heteroatom substitution, by such heteroatoms as N, S, 0, P, Si and B. Acrylic monomers contemplated to be within the scope of the present invention are those which conform to the formula: wherein each of R', R2, R3 and R4 are independently selected from hydrogen and carbon containing radicals having 1-20 carbon atoms. Examples of monomers which conform to the above formula include ethyl acrylate, methyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, hydroxyethyl acrylate, and the like, and mixtures of any two or more thereof. When a copolymerization is carried out, i.e., at least one comonomer is employed along with the monomer, the comonomer(s) can be present in any desired amount, i.e., from trace amounts up to a substantial excess with respect to the monomer employed. For example, it is sometimes desired in order to achieve desirable properties in the polymer product that a termonomer be employed in the polymerization process. Thus, useful polymer products are obtained when methacrylic acid is used as a termonomer in admixture with ethyl acrylate and methyl methacrylate. When a termonomer is employed, it is generally added in relatively small amounts, e.g., about 0.01 to 5 wt % based on the total weight of monomer (including comonomer and termonomer) charged. Preferably, the termonomer is charged in amounts ranging from about 0.1 to 2 wt %, based on the total weight of monomer charged. Those of skill in the art recognize that additional comonomers can be employed, so that copolymers comprising mixtures of three, four or more monomers satisfying the above definition are within the contemplation of the present invention. Suitable free radical initiators are well known in the art and can be readily chosen by the artisan. Exemplary materials include water soluble initiators, such as, for example, peroxygen compounds, especially inorganic persulfate compounds such as for example ammonium persulfate, potassium persulfate and sodium persulfate; peroxides such as for example hydrogen peroxide; organic hydroperoxides, such as for example cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, lauroyl peroxide; peracetic acid and perbenzoic acid; redox initiators wherein a water soluble reducing agent such as a ferrous compound promotes the decomposition of peroxides, persulfates and the like; as well as other free radical producing materials such as 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and the like. A wide variety of emulsifiers are useful in the practice of the present invention, as can readily be determined by one of skill in the art. Suitable emulsifying agents include cationic, anionic or nonionic emulsifiers or detergents customarily used in emulsion polymerizations. Representative types of emulsifiers are the alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, salts of high molecular fatty acids, amine soaps, alkaline metal salts of rosin acids, ethylene oxide condensates of long chain fatty acids, alcohols or mercaptans.
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