' Patented Feb. 7, i950 - 2,496,868 UNITED STATES PATENT‘ OFFICE 2,496,868 POLYMERS OF 3-VINYLPYRENE Ralph G. Flowers, Pitts?eld, Mass., assignm- to to General Electric Company, a corporation of New York No Drawing. Application May 13, 1948, ' , Serial No. 26,940 12 Claims. (Cl. 260—87.3) 2 This invention relates to polymers and co such as boron tri?uoride, are used. aperiod of polymers of vinyl compounds and to methods of time elapses between the addition of the catalyst , preparing same. More particularly, the inven and the beginning of the polymerization. This tion-ia concerned with new and useful composi tendency is particularly marked when the poly tions of matter comprising the product of poly merization is carried out at elevated tempera merization of a mass comprising 3-vinylpyrene. tures. A very large amount of solvent often in In my copending application, Serial No. 26,939, hibits or retards the polymerization of the mono ?led concurrently herewith and assigned to the mer or comonomers to the extent that polymer same assignee as the present invention, there are ization is not e?ected in a reasonable time. disclosed and claimed 3-vinylpyrene and methods 10 Another method which has been found effective - of preparing the same. I have now discovered in preparing the homopolymers and copolymers that this monomeric material may be polymer of the instant claimed invention includes ‘the ized or copolymerized with other polymerizable preparation of an intimate mixture of the mono compositions to yield valuable and useful com- ' meric materials by preparing a suspension or positions of matter. 15 emulsion of the monomer or mixture of mono As described in the above-mentioned applica mers in a liquid medium as, for example, water. tion, 3-vinylpyrene may be prepared by ?rst With speci?c regard to the polymerization of acetylating pyrene with an acetylating agent, for the monomer, 3-vinylpyrene, itself, it may. be example, acetic acid or anhydride, acetyl chlo said that the readiness and speed of the polymeri ride or bromide, ketene, etc., to obtain 3-acetyl 20 zation depend upon the purity of the latter. The pyrene. It is, of course, understood that by fur purer the monomer, the greater is the ease and ther acetylization of the monoacetyl pyrene, it rate of polymerization and the higher the molec is possible to prepare polymeriza'ble divinyl py ular weight of the polymer. The physical prop renes from diacetyl pyrenes by employing the erties of the homopolymer are, to a large ex same method as that used for preparing the 25 tent, dependent upon the polymerization. For monovinylpyrene from monoacetyl pyrene. The example, polymerizations carried out at high acetylated pyrene is then reduced or hydrogen temperatures at a very rapid rate usually result ated to form a hydroxyethyl pyrene which may in polymers of low molecular weight. In order then be dehydrated by contacting it with a de to obtain suitable polymerization products, care ful control of the polymerization reaction is hydration catalyst to obtain the monovinylpyrene, 30 more speci?cally, 3-vinylpyrene, which has a necessary. i melting point of 87° to 89° C. In producing the claimed homopolymer or co Various methods of ‘polymerizing the mono polymers, the polymerization of the monomer or meric 3-vinylpyrene, either by itself or with other monomeric materials may be carried out by means copolymerizable materials, may be employed, the , of heat alone, or it may be accelerated by means more desirable method depending largely upon of vinyl polymerization catalysts usually em the properties desired in the ?nal composition. ployed for the purpose. Examples of such poly For example, the monomer, either by itself or merization catalysts are oxygen, ozone, ozonides, with other copolymerizable materials, may be hydrogen peroxide, organic and inorganic acids dissolved in -a suitable inert solvent, for example, 40 and acidic- substances, e. g.,' hydrochloric acid. an aromatic hydrocarbon solvent (such as ben hydro?uoric acid, sulfuric acid, boron ?uoride, zene, toluene, inrlene, etc.) which is also a solvent stannic chloride, antimony pentachloride, the for any other members of the mixture. halogens, etc.; organic and inorganic peroxides, A small amount of solvent has little retarding for instance, peroxides of the aromatic acid series, effect upon, and in some cases actually acceler 45 e. g., benzoyl peroxide, tertiary 'butyl hydro ates. the polymerization of monomer or mono peroxide, tertiary butyl perbenzoate, l-hydroxy mers. A moderately large amount of solvent cyclohexyl hydroperoxide, etc.; peroxides of the tends to yield polymers and copolymers of short aliphatic acid series, for example, acetyl peroxide, chain lengths and often results in a period of stearyl peroxide, lauryl peroxide, etc.; sodium induction so that even when very active catalysts, 50 peroxide, barium peroxide, etc.; various per 2,498,868 compounds such as the persulfates, perchlorates, perborates, etc. Heat, light (ultra-violet light) its. Although the proportions, by weight, ordi or heat and light may be used with or without narily will be within the range of from 10 to 90 a polymerization catalyst in accelerating the per cent of the 3-vinylpyrene to 90 to 10 per cent polymerization. of other monomer or monomers, I do not intend 5 Where a catalyst is employed for accelerating to be limited to such range since other propor the polymerization, the catalyst concentration tions of the S-vinylpyrene and the other copoly may be varied, for example, within the range of merizable ingredient or ingredients may be high from 0.05 to 3 or 4 per cent or more, by weight, er or lower, for instance, from 1 to 99 per cent, of the polymerization mixture including the sol by weight, of the 3-vinylpyrene, to from 99 to 1 vent or suspension or emulsion medium if such per cent, by weight, of the other monomeric are employed. Where no such media are em material or materials. I may preferably employ ployed and the monomers or polymers are em a copolymerizable mixture containing, by weight, ployed alone, I have found it advantageous to from 1 to 75 per cent of the 3-vinylpyrene, based on the total weight of the copolymerizable in use from 0.1 to 2 per cent of the catalyst based gredients. on the weight of the total weight of the monomer or monomers used. 3-virwlpyrene can be cross-linked by com The most effective temperatures at which the pounds such as divinyl and diallyl compounds, polymerization may be effected lie within the e. g., divinyl and diallyl esters of diethylene range of from about 45° C. to 200° 0., preferably glycol, to form products that have increased heat from 60° C. to 150° 0., depending upon the pres 20 resistance and can be readily machined and ence or absence of solvents, the type of poly worked. Such products tend toward insolubility merizable materials employed, and the proper and infusibility as the per cent of the divinyl or ties desired in the ?nally polymerized product. diallyl compound is increased. The copolymers Greater polymerization speeds are obtainable at of 3-vinylpyrene with other vinyl compounds higher temperatures but this usually results in 25 containing only one CH2=C< grouping, many an undesirable reduction in the molecular weight examples of which have been given previously, of the ?nally polymerized product. It is usually are thermoplastic and can be treated, in general, advantageous to displace the air in the polymer as any thermoplastic material since they can be injection- or compression-molded, cast into ?lms, izable systems and in the free space above the oriented and fused. same with an inert atmosphere, for example, ni 30 trogen ‘or carbon dioxide. In order that those s killed in the art may ~ The homopolymers of this invention possess, better understand how the present invention in general, the physical properties of polystyrene may be practiced, the following examples are except that the softening point of the homo given by way of illustration and not by way polymer is considerably higher than the soften 85 of limitation. All parts are by weight. ing point of polystyrene. The electrical prop Example 1 erties of the homopolymer likewise compare to those of polystyrene, making it valuable for use Ten parts 3-vin ylpyrene was dissolved in 50 in electrical insulation. The homopolymers can, parts benzene an d 1.0 part benzoyl peroxide in general, be treated in the same manner as any added. The solution w as heated in an oil bath other thermoplastic material. They may be cast, at 100 C. for ?ve hours. The resulting Polymer pressed, extruded, rolled, machined and indec of 3-viny1pyrene, which was precipitated from tion-_ or pressure-molded. the benzene solution by diluting the latter with The homopolymer is, in general, compatible 45 methanol, had a softening point of 185° C. with the same materials as pohrstyrene. For example, it may be plasticized by the same plas Example 2 ticizers where softening point and strength are of secondary importance. Materials simulat A solution of 10 parts 3-vinylpyrene and 50 ing synthetic elastic products may be prepared 50 parts benzene was mixed with 1.0 part tertiary from these homopolymers by adding relatively butyl hydroperoxide and heated in an oil bath large amounts of plasticizers. at 100° C. for five hours At the end of this . The monomeric 3-vinylpyrene may be copoly time a white polymer was obtained as a precipi merized with a great number of copolymerizable tate from the benzene solution by the addition CH:=C<-containing compounds. Examples of “ thereto of methyl alcohol. such compositions of matter are dienes, e. g., butadiene, isoprene, piperylene, etc.; a vinyl Example 3 substituted aromatic hydrocarbon, e.