Patented Mar. 16, 1943 2,314,061

UNITED ‘STATES PATENT OFFICE‘.w 2,314,067 PROCESS FOR PRODUCING SULPHUR , DIOXlDE-OLEFIN RESINS Maxwell M. Barnett and John H. Brown, Jr., Port Sulphur, La., assignors to Freeport Sulphur Company, New York, N. Y., a corporation of Delaware No Drawing. Application February 3, 1939,. , Serial No. 254,386} 8 Claims. (Cl. 260-80‘) This invention relates to resins of the sulphur Another object is to provide a catalyst which dioxide-ole?n type and to a new and improved is more stable and safer to use than ‘many sub process for producing them. stances heretofore proposed and which is not li It has long been known that resinous poly able to undergo lexplosive decomposition. merization products may be produced under A further object of the invention is to provide proper conditions by the reaction of sulphur di- . a catalyst which can be made easily and which oxide with active unsaturated organic compounds avoids the use of low temperatures and solvents of the ole?n type, of which the mono-ole?ns like in its preparation. - ethylene, propylene, butene-l, butene-2, isobu Still another object of our invention is to pro tene, pentene-l and pentene-2 are examples. 10 vide an improved process for producing resins of Other examples of such unsaturated compounds the sulphur dioxide-olefin type, a catalyst being are butadiene, pentadiene and other conjugated used in this process which has no contaminating diole?ns; pentyne-l, hexyne-l and other acety or discoloring effect on the resin product, so that lenes; and ,poly-functional unsaturated com new products having superior qualities for mold pounds of the nature of allyl alcohol, vinyl acetate 15 ing and other purposes may be obtained. and allyl propionate. This reaction, however, Other objects and advantages of the invention takes place to a substantial extent only under may become apparent from the following descrip the in?uence of catalysts. When carried out tion. ' properly in the presence of a satisfactory cata According to the invention of Maxwell M. lyst, the reaction produces thermoplastic resins 20 Barnett, as disclosed in a copending application, that are valuable for use in the manufacture of Serial No. 254,381, ?led February 3, 1939, the molded objects, as bases for lacquers, varnishes, production of sulphur dioxide-ole?n resins is etc., and for other purposes to which plastics carried out by reacting sulphur dioxide with un are ordinarily applied. saturated organic compounds in the presence of The commercial development of resins of the active ozonides as catalysts, particularly an sulphur dioxide-ole?n type has been retarded by - ozonide that has been prepared under anhydrous the lack of sui?ciently active catalysts. Light of conditions. In that .process several of the ob‘ the proper wave length, oxidizing compounds jects. of the present invention are realized, but such as certain peroxides and silver nitrate, and disadvantages have been encountered due to the certain organometallic compounds have been dis 30 fact that the ozonide catalysts, in general, must closed heretofore as suitable catalytic agents. be prepared at very low temperatures and ex treme care must be exercised in handling and ' The known processes involve the reactor of sul using them because they are so unstable as to phur dioxide and an active unsaturated organic be dangerous. For example, the ozonides of compound, in a sealed glass tube or steel bomb, at comparatively low temperatures and in the ethylene and acrolein are so unstable that they are spontaneously explosive and are sensitive to presence of sunlight or another of these known slight shocks or rises in temperature. The catalysts. None of these catalysts, however, is ozonides of butene-l and butene-Z. are useful capable of converting the reactants into the de catalysts, but these materials must be prepared sired resinous product in an economically feasible at relatively low temperatures, and, while they period of time, many hours and even days being are not spontaneously explosive, a slight shock or required to obtain a satisfactory yield, and in elevation of temperature is sometimes sufficient "many cases resins are produced which are con taminated or discolored by the catalyst. to cause detonation. ' One of the objects of our invention is to secure It has been supposed that the catalytic activity a higher yield of resin than has heretofore been of the ozonides is proportional to the quantity of possible in the reaction between sulphur dioxide oxygen contained in the molecule. We have now and unsaturated compounds of the ole?n type by found, however, that in the case of diisobutylene providing an exceedingly active catalyst for the ozonide the catalytic activity isI considerably greater than would be indicated by comparing reaction. . Another object of our invention is to provide 50 the quantity of active oxygen in the molecule with ’ . a catalyst for the reaction which results in a the quantity of active oxygen in the molecule of high yield of resin within a very short period other catalytically active ozonides. We have also of time as compared with prior processes, periods found that diisobutylene ozonide is quite stable of an hour or less being required in accordance in comparison with other ozonides and is not li with this invention, instead of hours or days. able to undergo explosive decomposition. Thus, 2,314,067 this material may be prepared and handled safely the use of very small amounts of the catalytic without requiring special precautions. and it may agen _ ,. be stored for extended periods of time, under con The production of the sulphur dioxide-ole?n ditions that are easy to maintain, without sub resin, using diisobutylene ozonide as the cata stantial disintegration or loss of catalytic activity. lyst, may be carried out as .follows: The proper Furthermore, diisobutylene ozonide may be heated‘ quantity of catalyst, say 25% of the weight of to relatively high temperatures without explosive resin which theoretically can be obtained from decomposition. the sulphur dioxide-ole?n reaction, may be Another important feature of our invention re weighed and dissolved in a small quantity of an sides in the provision of a catalyst for the sulphur alcohol, or a solution of known concentration dioxide-ole?n reaction which possesses extraor may be made in an alcohol or other suitable sol dinary catalytic activity and at the same time is vent and an aliquot taken. The diisobutylene quite simple to prepare. In contrast to other ozonide or solution thereof is added to a mixture ozonides, diisobutylene ozonide can be prepared ' of sulphur dioxide and ole?n in a reaction ves at room temperatures, whereas most of the other sel. If the mixture is at a temperature such catalytically active ozonides require cooling to that it possesses appreciable vapor pressure, the _ temperatures much below normal temperatures in catalyst should be ,forced into the vessel with the course of their preparation. pressure. For most rapid reaction, the temper According to the present invention the pro ature of- the» reaction mixture should be above duction of resinous polymerization products 20' 0° C. . through the reaction between sulfur dioxide and After ‘the introduction of the diisobutylene active unsaturated organic compounds, such as ozonide there is an induction period during which mono-ole?nes, is practiced in a commercially feas no perceptible reaction takes place. This induc ible manner,-with large yields, a short reaction _tion period is much shorter according to our period and products free from undesirable con process than when using known catalysts, and tamination or discoloration,—by carrying out the may vary from a few seconds to a few minutes, ’ reaction in the presence of diisobutylene ozonide from 1 to 2 minutes being the usual duration. as a catalyst. Once started, the reaction proceeds rapidly and The resins produced in the practice of this is substantially complete within one hour. ‘ process are remarkably free from contaminants 30 The addition of the catalyst to the reaction affecting their color or clarity when molded. The mixture ordinarily takes place in a single oper- , product obtained from the container in which the ation, the vessel then being sealed. This step, reaction has taken place, after washing or other 7 however, may be carried out in other ways, for vtreatment to remove excess reagents, is capable of example, by adding the catalyst in portions as ' being molded into hard; tough and stable objects - the reaction proceeds. . . which are normally colorless and transparent. The process of our invention may be carried The product is also valuable as a molding ma out in other ways, 'and, as .long as the diiso terial with or without added substances such as butylene ozonide is prepared in ‘the proper con ?llers, dyes and color pigments, as a constituent dition and used in the proper concentration, the of lacquers, paints, adhesives and other coating 40 speci?c manner in which it is used can be varied compositions, and as a plastic in various ?elds to suit the conditions and characteristics of the in which other known plastic materials are em various reagents employed. ployed. The following examples further illustrate suit According to the preferred embodiment of the able manners of practicing our invention, invention, the catalyst employed for the reaction is ‘substantially pure diisobutylene ozonide that Example I has been prepared under substantially anhydrous A mixture of butene-2 and $02, in the molar conditions. We have found that the prepara ratio of 123, is introduced into a glass container tion of the ozonide and its qualities when intro and cooled with dry ice and ether. A weighed duced into the reaction mixture have important quantity of diisobutylene ozonide, dissolved in a e?ects on the reaction, and that optimum results volume of ethyl alcohol corresponding to 5% of are obtained only when following this preferred the volume of the reaction mixture, is then add embodiment of the invention. ed. The quantity of ozonide used corresponds to The preparation of the improved catalyst may 0.5% of the weight of resin theoretically obtain be carried out by passing dry'or substantially 55 able. The container is sealed off and placed in anhydrous ozonized oxygen or air into dry liquid a water bath maintained at 0-10° C. These lim diisobutylene until no more absorption of ozone its are not critical, but better yields are obtained takes place, which indicates the point of complete if the temperature is not allowed to rise too high. conversion to diisobutylene ozonide. In practice, The reaction begins within one to two minutes it is advisable to keep the diisobutylene below 10° 60 and results in a conversion of 72% of the ole?n C. to minimize evaporation losses, although this to polymer in 10 minutes, ‘and substantially 100% is in no sense necessary for the ozonization reac conversion in onehour. ‘tion. The catalyst is ready for use when the ab sorption of ozone has ceased. Example 11 We have found that the sulphur dioxide ole?n A glass‘ container is cooled with dry ice and reaction may be carried out in the presence of as ether, and a mixture of b'utene-l and-SO: in the low as .01% by weight of the diisobutylene ozonide molar ration of 2:1 is introduced. A quantity catalyst. Increasing amounts of the catalyst are of diisobutylene ozonide, corresponding to 0.5% e?ective in increasing the yield and velocity of of the weight of resin theoretically obtainable, the reaction until an optimum quantity is .at 71 is dissolved in a small quantity of ethyl alcohol tained, which is ordinarily from about .5 to about and added to the cooled mixture of SO: and ole 1%, by weight. Further increase in the quantity ?n. The‘container is sealed off and placed in a of the catalyst, beyond about 1%, ordinarily fails water bath at 0-10° C. Reaction begins within to increase either the yield or velocity of the reac two minutes and results in the conversion of tion, so that optimum results may be secured by 75 85% of the S0: to resin in one hour. 2,314,067 3 The resins produced in the practice of our has been prepared under anhydrous conditions, ‘ process are not discolored or contaminated by carrying out the reaction in a sealed container, the catalystor its decomposition products, and and. cooling .the container attemperatures be in general they may be molded at lower temper tween 0° C. and room temperature during the atures than resins prepared with other catalysts course of the reaction. which have been proposed heretofore. Upon 4. The process for producing resins of the sul molding these resins, colorless transparent ob- phur dioxide-olefin type which comprises react ing sulphur dioxide and an ole?n in the pres jects are obtained which are hard, tough and ence of substantially anhydrous diisobutylene stable. Particular detailsv and examples have been 10 ozonide, the reaction mixture initially containing described in this speci?cation in order clearly from about .01% to about 1.0% diisobutylene to set forth suitable manners of practicing our ' ozonide, by weight. 5- The process for producing resins of the sul invention. The invention is not restricted to phur dioxide-ole?n type which comprises intro these, but should be accorded a scope commen ducing substantially anhydrous diisobutylene surate with its contributions to the art as lim ited only by the requirements of the appended ozonide into a vessel containing sulphur dioxide and an ole?n, sealing the vessel, and permit claims. ting the resulting polymerization reaction to pro We claim: , i 1. The process for producing resins of the sul ceed. ' phur dioxide-ole?n type which comprises react 6. As a new product of manufacture, a sulphur ing’ sulphur dioxide and a compound selected dioxide-ole?n resin free from catalytic discolor from the group consisting of ole?ns, pentyne-l, ation consisting of the product of the reaction hexyne-l, allyl alcohol, vinyl acetate and allyl between sulphur dioxide and ole?n in the pres propionate in the presence of diisobutylene ence of diisobutylene ozonide. 7. As a new product of manufacture, sulphur ozonide as a catalyst. 2. The process for producing resins of the sul dioxide-butene-2 resin free from catalytic dis phur dioxide-ole?n type which comprises react coloration ‘consisting of the product of the re ing sulphur dioxide and a compound selected action between sulphur dioxide and butene-2 in from the group consisting of ole?ns, pentyne-l, the presence of diisobutylene ozonide. hexyne-l, allyl alcohol, vinyl acetate and allyl 30 8. As a new product of manufacture, sulphur propionate in the presence of diisobutylene dioxide butene-l resin free from catalytic dis ozonide that has been prepared under substan coloration consisting of the product or the re tially anhydrous conditions. action between sulphur dioxide and butene-l in 3. The process for producing resins of the sul the presence of diisobutylene ozonide. phur dioxide-ole?n type which comprises react 35 ing sulphur dioxide and an ole?nic compoundrin MAXWELL M. BARNETT. the presence of active diisobutylene ozonide that JOHN H, BROWN, .m.