Патент USA US2406260код для вставки
Patented Aug. 20, 1946. 2,406,260 UNITED} STATES PATENT OFFICE 2,406,260 POLYSULPHJDE POLYBIER Laurence L. Ryden, Midland, vMich, assignor to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing. Application December 3, 1943, Serial No. 512,774 13 Claims. . (Cl. 260-78) 1 This invention is concerned with polysulphide nearly resembles natural 2 rubber than organic . polymers and is particularly directed to a method for the preparation of cold-?ow resistant organic polysulphide polymers heretofore known. , The exact mechanics of the reaction are not polysulphide polymers and to the polysuiphide , understood, and it is not desired that the inven tion be in any way limited by theory as tohow Organic polysulphide polymers have been sug such result is accomplished. However, it seems polymer product so obtained. reasonable to assume that the provision of free gested for use and found valuable in a Wide hydroxyl groups along the chain oithe polymer variety of applications. These materials are em as initially formed'permits of coupling or cross ployed in some instances as substitutes for nat ural rubber and in others as distinct elastomer 1G. linking upon reaction with the unsaturatedpoly basic acid or acid anhydride whereby a compact products differing from rubber in. such a manner molecule is obtained which is resistant to. defor as to be preferable thereto. The cold-?ow prop mation under pressure, a property not shared by the conventional polysul-phide chain structures. restricted their use. Thus thesematerials un In carrying out the invention, the condensa dergo deformation under pressure and show but tion between the aqueous alkaline polysulphide a slight recovery. This prohibits their use in and organic reactant may be accomplished in situations where high elasticity and resistance any suitable manner, provided only that such to flow are desirable. reactants and amounts. be employed as yield a A voluminous art has accumulated with respect to the preparation of organic polysulphide poly 20 product of rubbery consistency. Thus the or ganic reactant may be added all at once'to the v mers. Rubber-like materials have been prepared by reacting aqueous alkaline polysulphides with ' polysulphide solution or such addition may be erties of the polysulphide polymers have greatly a very wide variety of organic halides and‘ par ticularly di-halo-alkanes such as ethylene chlo ride, propylene chloride, and other aliphatic portionwise with stirring to ‘accomplish “piece meal reaction of ‘ the materials. The temper 25 atures, concentrations, and‘other conditions 'of reaction may be regulated as required. Similarly ‘the reaction of ‘the polysulphide polymer with the polybasic acid‘ or anliydride coupling agent may be accomplished in any suitable fashion. issued December?, 1932; 1,923,392; issued August 30 Representative conditions of reaction for the compounds containing -—CH2— radicals and a multiplicity of halogen atoms. Representative of the teachings of the art is the disclosure found in United States Letters Patents Nos. 1,890,191, condensation and coupling‘ or‘curing operations 22., 1933; Reissue 19,207, issued June 12, 1934;. 2,142,144, issued January 3, 1939; and 2,195,380, issued March 16, 1940. Each of these patents dis closes a large number of e'lastomer products all subject to the disadvantages as outlined above with respect to cold-?ow. It is an object of the present invention. to pro vide a method for the production of an organic polysulphide polymer product which will be re are set forth in U. S. Patent No. 2,195,380, ‘to Joseph C. Patrick, dated March’ 26, 1940. The preferred embodiment of theinvention re sides in the use of glyceryl-dichlorohydrin in an initial condensation with aqueous sodium poly ~ This chlorohydrin material» has» givenv good results when employed in mixture with other sulphide. aliphatic halogen compounds-and particularly the sistant to cold-?ow and deformation. It is a 40 lower alkylene halides. The amount of the glyc eryl-dich-lorohydrin employed is between about 1 further object to provide .a such polysulphide ' and 20 mole per cent of the total organic react polymer product which will have better proper ant concerned. The balance of- the organic re ties of recovery than characterize known polymer actant consists preferably‘ of a mixture off-ethyl products of this type. Other objects will become apparen't'fr'om the following speci?cation. I have discovered that a resilient polymer re sistant to cold-flow is obtained by a modi?cation of the usual procedure for the preparation of ene, chloride and propylene chloride, with ‘the former predominating. When too high a' propor‘ tion of glyceryl-dichlorohydrin is employed, the polymer obtained does not have rubber-like prop erties. When too little is used, the desired'cold flow resistant characteristic is not obtained in the organic polysulphide elastomers. This desirable result’ is accomplished by carrying out the con densation of the aqueous alkaline polysulp-hide The- preferred coupling agent for reaction with the basic polysulphide polymer is maleic anhye with a mixture of’ (1) a halohydrin comprising two dride. This reactant is employed in the amount Y‘ halogen atoms and at least one hydroxyl all attached to aliphatic carbon atoms and (2)v other 55 of at least'5 per cent and preferably not‘ to ex ceed 40 percent by Weight of the glyceryl-dii polyhalo-aliphatic compounds to form an elasto mer product, and thereafter reacting such prod One mode of operation which has been found ’ uct with an alkenedioic acid or alkenedioic acid particularly satisfactory consists of reacting. a anhydride. The resulting material has good re sistance to cold-?ow, and in this respect more 60 molecular excess of NazSLs-awith lI'mole‘ of; a ?nal product. chlorohydrin. I I ' ' " ‘ -. ‘ ' 2,406,260 7 . 3 , V . elastomer in which onlyfone part Weight of maleic anhydridewas employed. Here also there mixture of glyceryl-dichlorohydrin and lower, al kylene chlorides,the former beingpresent in the was" obtained a'rubber-like material; ' , ‘ amount of from about 5 to 20 mole per cent. The reaction is carried, out by dissolving the polysulr. H ,Cylindrical plugs 1/2 inch high by 1/2 phide in water and adding the organic reactants "5 *in' diameter 'were prepared from the elastomer. mixture and also from the portionwise to the polysulphide solution with stir ring at between 65° and 80f’_ c. Thepmixture ,i_s__ pomposition. in' mixture 'with 5 parts 'warmed and stirred at '70°-80° 1C. for janfaddi-7; hone‘;' part ‘of maleic ‘anhydride. ~ tional hour, and thereafter subjected ‘to treat- 7 ment with an aqueous solution of 0.2 mole of'a " were fthenycured at 298° F. for 16 vvThese test The _ inch basic basic and plugs 15 minutes. pieces‘ were employed to determine high. ranking sodium polysulphide ~_(Na2S4.5 g-or _' the resistance to cold-?ow of the several mixtures. In'ithis operation each plug was compressed to '75 per .cent of its original height for onerhour at higher) at a temperature of between 785° and-110?’? .7 ' C. The resultant latex is Washed with water, a temperautre of 70° C. and the extent of recov~ coagulated with dilute acid, separated, and dried: ’ ' _While any suitable means may be employed to .15 cry of each determined upon the release of pres react this initial elastomer product with the acid or acid‘anhydride couplingagent, theipr'eferred sure. From an initial‘ compressionto- 0.375 inch, the "plug made ‘up from the unmodi?ed elastomer‘ vmethod consists 'of-mixing the product with'the composition recovered only 2 per cent to a height ~ acid or anhydride on the rolls of a conventional rubbericompounding mill. This is conveniently‘ accomplished by ?rst modifying the polysulphide ' of 0.377 inch. 'The plug preparedfrom the elas 20 tomer reacted with one part vof maleic anhydride' recovered to the extent of 33 ‘per-cent tov 0.421 polymer product with additaments such as zinc inch, and the plug made up from the elastomer oxide,’ carbon black, and/or other ?llers,’ sta? reacted with 57 parts of maleic anhydride recov bilizers, and theilike, and then mixing and milling‘ thevcoupling agent ‘therewith. During" this and _ ered to the extent of 62 per cent to 'a height of 0.453 inch. ‘A control plug prepared'irom a basic the subsequent, step of curing at temperatures composition containing an elastomer obtained by the reaction of sodium polysulphide, withv the‘ above 250°; F., a reaction takes place between the crude polymer product and the coupling agent _ alkylene'ha'lides in the absence of glyceryl-di . chlorohydrin had 0 per cent recovery. ‘ x whereby the desired cold-?ow resistant and re silient polymermaterialis produced. _ 25 ' V . Example 2 The following examples illustrate the practice Ina similar fashion a mixture of ‘6.9 parts‘ by weight (0.06 mole) of propylene chloride, 69' limiting. ,' V ' P parts (07 mole) of ethylene chloridei and 22 35 parts (0.17 mole) of glyceryl-dichlorohydrin was A mixture of '7 parts by weight (0.06 mole) of reacted with a mixture of '94 parts by weightv (1_ of the. invention but are not to be construed as - .Egra’mplel,‘ _ . . ' propylene chloride, '75 parts (0.76 mole) ofiethyl mole) of NaZSLS, 2 parts of a sodium salt of sul ene chloride, and 12 parts (0.09 mole) of 'glyceryl dichlorohydrin was added portionwise and with phonated ethyl oleate (Igeponap),§6 parts ‘of freshly precipitated magnesium hydroxide,v and stirring over a period of one .hour to a dispersion 40 500 parts of water. The initial reaction,'subse in 500 parts of water of 94' parts by weight‘ (1.0 quent treatment with high'ranking' sodium poly-J sulphide (Nazsfrs) , coagulatiomand separation all‘ mole) of Na2S1;5,'2 parts of'sodium-alkyl-naph4 thalene-sulphonic acid (Nekal BX), and '6 parts were substantially‘ as described in Example ‘11 with therecovery of a substantial yield of dried The temperature of the‘ reaction mixture‘ was 45 elastomer. 100 parts of elastomer were com maintained‘at' about 70’ C(during the addition‘. pounded as follows: ' v ‘, V i ‘ ~ of "freshly precipitated magnesium hydroxide. Stirringand warming of the mixture at 770°-80° Material: C. was continued for one hour. A'solution'of 38 _ ' Parts by weight parts‘ by weight of Nagsit in 100 parts of water Elastomer ____ __-__; _______________ __ was then added to the mixture and/stirring con Carbon black ____________ __-e___-_______ tinue'd'for?an additional'hour, the temperature" Stearic acid ___________ __- ______ __'____ 0.5 mMercaptobenzothiaz'ole v__-___>___~_____‘_ . ‘2.0 ,Diphenylguanidine 1____'_L___;_.____,__‘ 0.1 . being maintained at about 90° C. vThe resultant ' latex was washed several'times 'with'water and coagulated with dilute sulphuricacid. 4 The‘ solid, ' i The dried elastomer was then the following basic mixture: " - ' 60 - ' This basic composition was mixed with 5 parts‘ of maleic anhydride and cured-at 274° *F. for 1 product of reaction was separated’fro'm the'liquid components of‘ the mixture and dried to- obtain 60 parts by weight‘ of ‘elastomer. 100 minutes Cylindrical to obtain plugs awere rubber-like made upproduct.’ from the basic . ' elastomer mixture and from such mixture'fol compounded in ' ' lowing- modi?cation with ‘maleic 'anhydride. 60 These plugs werev cured at 274°F. for 15 minutes ,- ~ and ‘subjected to compression as previously de scribed.‘ The plug made up from the basic com position showed a. 2 percent recovery to a height Carbon "black _________ __:_ _________ __ .60} 0.377inch. The. plugfrom the modi?ed elas vStearic acid _____ _'_ __________ __V_____-_ 0.5 Mercaptobenzothiazole ______ __-__;__; v2.0 65 tomer product recovered to a height of 0.465-inch, Zinc~oxidegs____;s___s_e ____ _-_ ____ __‘ 107., or,72 _ This composition‘ was then reacted:with"5‘part_s by‘weight'of maleic anhydride by cold mixing ‘on the rolls‘of a conventional rubber-compounding mill and subsequent curing of the mixture for 15 minutes at 298° F. to obtain the desired‘rubber-v like polymer product‘. ' ' A similar mixing and curing operation was car ried out with an additional quantity of the dried per cent. 7 _ ' , I While the foregoing examples have been .di rected speci?cally to operations in which the cross-linking or coupling is accomplished. with 70 maleic anhydride, it‘ is to be understood that equivalents therefor may also be employed. Rep resentative of the acids and anhydrides poten-J tially adapted for'such use are maleic acid, citra conic acid and; anhydride, glutaconic acid and anhydride, pyrocinchoninic acid . anhydride, 2,406,260 6 ethyl maleic acid and anhydride, methyl ethyl from about 5 to about 40 per cent by weight maleic acid and anhydride, xeronic acid and an of the hydride, methyl glutaconic acid and anhydride, etc. Also other polyhalo-aliphatic compounds thereafter heating the mixture to obtain the de sired rubber-like composition. may be substituted, wholly or in part, for the ethylene chloride and propylene chloride dis-' polysulphide polymer product prepared accord 6. A cold-?ow resistant rubber-like organic ing to the process of claim 5. 7.‘ A method for the preparation of cold-?ow , closed. Representative of such materials are bu- ' tylene chloride, B,B’-dichlorodiethyl ether, 1.3 trimethylene chloride, dichlorobutylene, etc.‘ I claim: . glyceryl-dichlorohydrin employed,_ and - resistant rubber-like organic polysulphide poly 10 mers, which includes the steps of condensing a ' 1. A method for the preparation of cold-flow resistant rubber-like organic polysulphide poly molecular excess of an alkaline polysulphide with a mixture of (1) from 1 to 20 mole per cent of a halohydrin comprising two halogen atoms and, mers, which includes the steps of condensing .a molecular excess of an alkaline polysulphide with at least‘ one hydroxyl all attached to aliphatic a mixture of (1) from 1 to 20 mole per cent of a 15' carbon atoms in (2,) a polyhalo-aliphatic com halohydrin comprising two halogen atoms and’ pound containing at least one —CH2- radical, .to form an elastomer product, thereafter com carbon atoms in (2) a polyhalo-aliphatic com-‘ pounding such product with one of the group . pound containing at least one -—CI-I2 radical to consisting of alkenedioic acids and anhydrides form an elastomer product, and thereafter com 20 in the amount of from about 5 to, about 40, per pounding such product with one of the group cent of the halohydrin employed, and heating the consisting of alkenedioic acids and anhydrides in mixture to obtain the desired rubber-like com the amount of from about 5 to about 40‘ per cent by weight of the halohydrin employed. . ' 8. A method for the preparation of cold-?ow 2. A method for the preparation of cold-?ow 25 resistant rubber-like organic polysulphide poly resistant rubber-like organic polysulphide poly mers, which includes the steps of condensing a mers, which includes the steps of condensing a molecular excess of an alkali-metal polysulphide at least one hydroxyl all'attachedto aliphatic position. molecular excess of an alkali-metal polysulphide with a mixture of (1) from 1 to 20 mole per cent - v ' with a mixture-of (1) from 1 to 20 mole per cent - of glyceryl-dichlorohydrin in (2), a lower alkyl of glyceryl-dichlorohydrin in (2) a lower alkyl 30 ene halide to form an elastomer product, there after compounding such product with one of the ene halide to form an elastomer product, and thereafter compounding such product with one‘ group consisting of alkenedioic acids and anhy-J, drides in the amount of from about 5 to about ’ of the group consisting of alkenedioic. acids and 40 per cent by weight of the glyceryl-dichlorohy-' V anhydrides in the amount of from about 5 to 40 per cent by weight of glyceryl-dichlorohydrin drin employed, and heating the mixture to ob- ' ‘ employed. , I 3. A method for the preparation of cold-?ow resistant rubber-like organic polysulphide ,poly i ‘ tain the desired rubber-like composition. 9. A method for the'preparation of cold-?ow resistantrubber-like organic polysulphide poly mers, which includes the steps of condensing a molecular excess of sodium polysulphidewlth a 40 molecular excess of sodium polysulphide with a mixture of (1) from 1 to 20 mole per cent of mixture of (1) from 1 to 20 mole per cent of glyceryl~dich1orohydrin in (2) an alkylene hal glyceryldichlorohydrin in (2) an alkylene halide product consisting of about 90 per cent ethylene ide product consisting of ab0ut90 per cent ethylg ene chloride and about 10 per cent propylene chloride and about 10 per cent propylene chlo chloride to form an elastomer product, and ride to form an elastomer product, thereafter compounding such product with an alkenedioic thereafter compounding such product with an alkenedioic acid anhydride in the amount of acid anhydride in the'amount of from about 5 to about 40 per cent by weight of the glyceryl-di from about 5 to 40 per cent by weight of‘g1ycery1 mers, which includes the steps of condensing a ' chlorohydrin employed, and heating the mixture ' 1 ' 4. A method for the preparation of cold-?ow 50 to obtain the desired rubber-like composition, resistant rubber-like organic polysulphide poly 10. A method for the preparation of cold-?ow mers, which includes the steps of condensing a resistant rubber-like organic ‘polysulphide poly molecular excess of sodium polysulphide with a mers, which includes the steps of condensing a mixture of (1) from 1 to 20 mole per cent of ‘molecular excess of sodium polysulphide with a glyceryl-dichlorohydrin in (2) an alkylene hal mixture of (1) from 1 ‘to 20 mole per cent of ide product consisting of about 90 per cent ethyl glyceryldichlorohydrin in (2) an alkylene halide ene chloride. and about 10 per cent propylene product consisting of about 90 per cent ethylene dichlorohydrin employed. chloride to form an elastomer product, and thereafter compounding such product with ma leic acid anhydride in the amount of from about 5 to 40 per cent by weight of glyceryl-dichloro hydrin employed. 5. A method for the preparation of cold-flow resistant rubber-like organic polysulphide poly mers, which includes the steps of condensing a molecular excess of sodium polysulphide with a mixture of (1) from 5 to 20 mole per cent of glyceryl-dichlorohydrin in (2) an alkylene hal chloride and about 10 per cent propylene chlo ride to form an elastomer product, and there after compounding such product with maleic acid anhydride in the amount of from about 5 to about 40 per cent by weight of the glyceryl-di chlorohydrin employed, and heating the mixture to obtain the desired rubber-like composition. 11. A cold-?ow resistant rubber-like organic polysulphide polymer product prepared accord ing to the process of claim '7. a 12. A cold-?ow resistant rubber-like organic ide product consisting of'about 90 per cent ethyl polysulphide polymer product prepared accord ene chloride and about 10 per cent propylene ing to the'process of claim 9. chloride to form an elastomer product, mixing this elastomer with carbon black and vulcaniz 13. An uncured organic polysulphide elas tomer product prepared according to the proc ing accelerators, mixing with such elastomer composition maleic anhydride in the amount of ess of claim 1. ' LAURENCE L. RYDEN'.