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United States Patent Office Patented Nov 3,410,836 United States Patent Office Patented Nov. 12, 1968 1. 2 matic ketone when reacted with lithium metal in an 3,410,836 POLYMERIZATION OF CONJUGATED DIENES etheral solvent forms a complex in which one of the WITH AIDLITHIUM COMPLEX OF AN ARO. lithium atoms is bonded to the oxygen of the ketone and MATIC KETONE another lithium atom is bonded to the ketyl carbon. We Henry L. Hsieh and William J. Trepka, Bartlesville, Okla., have concluded that the initiator itself becomes a part assignors to Philips Petroleum Company, a corporation of the polymer and that polymer growth takes place only of Delaware at the carbon-lithium bond because when the polymer is No Drawing. Filed Mar. 9, 1964, Ser. No. 350,601 recovered in a conventional manner with an alcohol or 11 Claims. (CI. 260-83.7) acid, thereby replacing any lithium present in the polymer with hydrogen atoms, the polymer which results contains O hydroxy groups. It was quite surprising that the dilithium ABSTRACT OF THE DISCLOSURE complex should behave in this fashion because the re Polymers of conjugated dienes containing terminal action product of sodium and aromatic ketones polym hydroxy groups are made with a dilithium complex of erizes a vinylidene-containing monomer by a free radical an aromatic ketone followed by treating the polymer to mechanism with no indication of achieving the results remove the lithium atoms. obtained in the present invention. It is an object of our invention to provide a method -wallow" was of polymerizing vinylidene-containing monomers. An This invention relates to the polymerization of vinyli at the carbon-lithium bond because when the polymer is dene-containing monomers. In another aspect it relates 20 other object is to provide a method of preparing a poly to a process for preparing polymers which contain re mer which contains a hydroxy radical. Another object is active groups. to provide a method of preparing polymers of mixed It is known that reactive polymers can be made by functionality. Still another object of our invention is to polymerizing conjugated dienes with an organo-alkali provide a method of forming polymers which can be metal initiator and terminating the polymerization in such coupled and cured by reactions with polyfunctional or a way that the alkali metal atoms present in the polymer ganic compounds. Other objects, advantages, and features are replaced by reactive groups. For example, butadiene of our invention will be apparent to those skilled in the can be polymerized in a hydrocarbon diluent with an art from the following discussion. initiator such as 1,4-dilithiobutane and when the mono The polymerization initiators which are used in this mer has been consumed the polymerization mixture re 30 invention are the dilithium complexes of aromatic ketones acted with carbon dioxide and then with a proton donor, and are formed by reacting lithium metal in the form of such as an alcohol or an acid, to produce a polymer con wire, chunks, or the like with an aromatic ketone in an taining carboxy groups. Because of the progress of the etheral solvent. Suitable solvents include diethyl ether polymerization reaction mechanism as it is now under and diisopropyl ether, tetrahydrofuran, dioxane, or the stood, the reactive groups are positioned terminally on like or mixtures of Such ethers. The aromatic ketones the polymer chain. In this way a polymer containing a are preferably hydrocarbon except for the oxygen of the carboxy group on each end of the molecule can be pre carbonyl group and can contain up to 50 carbon atoms pared and such polymers have been called, for the sake in the molecule. The preferred aromatic ketones are repre of convenience, "telechelic' polymers or, in this specific sented by the formula instance, “carboxy-telechelic polybutadiene.” Using the 40 same terminology, a polymer having a reactive group on only one end of the polymer chain would be a "semi telechelic' polymer. in which R and R' are each a phenyl radical, a 1-naphthyl Telechelic and semi-telechelic polymers, as above de radical, a 2-naphthyl radical, or such radicals which con scribed, are very useful because they can be cured by 45 tain substituents inert with respect to the lithium. Ordi reacting them with a variety of polyfunctional com narily any substituents should be hydrocarbons and pref pounds. For example, the carboxy-containing polymers erably are lower alkyls, that is, alkyl groups having from can be coupled with polyisocyanates or with polyhydroxy 1 to 4 carbon atoms. We further prefer that no more than alcohols. Liquid or semi-solid polymers can very readily three such substituents be attached to each R or R' group. be converted into solid products under conveniently con 50 Examples of such aromatic ketones represented by the trolled conditions. In preparing polymers which are capa formula given above include benzophenone, phenyl 1 ble of coupling or crosslinking with polyfunctional com naphthyl ketone, di-2-naphthyl ketone, di-4-tolyl ketone, pounds, it is frequently desirable that more than one kind di-4-isobutylphenyl ketone, di-2,4,6-trimethylphenyl ke of reactive group be present in the polymer so that the tone, 4-methyl-7-ethyl-1-naphthyl 2-methyl-6-propyl-1- coupling reactions can be effected in stages or so that a 55 naphthyl ketone, di-4,5,7-tri-n-butyl-2-naphthyl ketone, 2 wider selection of coupling compounds is possible. Diffi styl-5-propylphenylike. 6-methyl-2-naphthyl ketone, and the culties are often encountered in preserving the terminally In preparing the initiators an excess of lithium is used positioned alkali metal atom in the polymer until it can and the temperature is normally in the range of -50 to be replaced with a reactive group. Any impurity in the 150°C., preferably from 0 to 100° C. Room temperature reaction mixture which can contribute a hydrogen ion 60 is satisfactory. The initiator which is formed by this reac tends to reduce the functionality of the final product so tion can be represented by the formula that the theoretical ideal of each polymer molecule con taining two reactive end groups is not achieved. Li We have discovered that polymers of increased func 65 tionality or polymers containing different functional R--ROL groups can be made by using an initiator of a specific in which R and R' are as previously defined. In the polym type. According to our invention, reactive polymers are erization reaction the polymer growth occurs at the car prepared by contacting a vinylidene-containing monomer bon-lithium bond while the -OLi group in the initiator under polymerization conditions with a dilithium complex 70 remains unchanged. During the recovery procedures in of an aromatic ketone and treating the polymer formed which the polymer is contacted with a proton donor, the to remove the lithium atoms. We have found that an aro lithium atom of the -OLi group is replaced with hy 3,410,836 3 4 drogen, thereby resulting in the formation of a hydroxy amount of initiator can vary considerably but is normally group which is attached to the carbon atom which was in the range of about 0.5 to 200 millimoles per 100 grams bonded to the oxygen in the ketone. of monomer. The preferred range for initiator level is The monomers which can be polymerized by the initia from 1 to 150 millimoles per 100 grams of monomer. tors described herein are those which contain a vinylidene The polymerization mixture should be agitated and the group which is attached to a carbon atom multiply bonded reaction time can extend from a few minutes to 100 hours to another atom. Normally these monomers will not con or more. Usually a short induction period is required. tain over 30 carbon atoms per molecule and will be hy Conversions can be expected to be nearly quantitative drocarbons except that the monomers can contain a when using a hydrocarbon diluent. At the end of the reac halogen, oxygen or nitrogen atom but are free from reac tion the initiator can be inactivated and the polymer coag tive hydrogen atoms. We prefer to use conjugated dienes O ulated by adding an acid or alcohol. The polymer is then containing 4 to 12 carbon atoms and more preferably 4 to separated, washed and dried using conventional recovery 8 carbon atoms per molecule. Examples of such con techniques. jugated dienes include 1,3-butadiene, isoprene, 2,3-di When the polymer is directly recovered by treating with methyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2 a proton donor such as water, an alcohol or acid, the phenyl-1,3-butadiene and the like. Conjugated dienes con polymer recovered contains a single hydroxy group on or taining halogen and alkoxy substituents such as chloro near one end of the polymer molecule. The proximity of prene and 2-methoxy-1,3-butadiene can be used. The con this hydroxy group to the end of the polymer molecule jugated dienes can be formed into homopolymers or co depends upon the size of the R or R' group in the aro polymers including block copolymers prepared by charg 20 matic ketone. When these groups are unsubstituted or ing the monomers sequentially. lower alkyl-substituted aryl groups, this hydroxy group Also included among the vinylidene-containing mono can be considered terminal. Prior to termination of the mers are the vinyl-substituted aromatic compounds such polymerization with a proton donor, a reactive lithium as styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and atom is present at the other end of the polymer chain and the alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, aryl 25 can be replaced with a functional group by treating the oxy, and dialkylamino derivatives thereof in which the polymer with a suitable reagent.
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