Preparation of polymerized vinyl alcohol

Abstract

Claims

UNITED STATES PATENT OFFICE PREPARATION OF POLYIVIERIZED VINYL ALCOHOL Herbert Berg, Burghausen, Upper Bavaria, Germany, assignor to Chemische Forschungsgesellschaft m. b. H., Munich, Germany, a corporation of Germany No Drawing. Application May 5, 1938, Serial No. 206,272. In Germany May 10, 1937 20 Claims. (01. 260-90) This invention relates to a process for the prodiflicult to separate such excess alcohol from the duction of polyvinyl alcohol and partial derivaester formed in the reaction. Thus, when polytives thereof. vinyl acetate is hydrolyzed in methanol solution,a The conventional method of preparing polymixture of methanol and methyl acetate is ohmerized vinyl alcohol is by the saponification of tained. Since these two compounds form a low- 5 polymerized vinyl esters or of other saponifiable boiling binary mixture, the constituents cannot polymerized vinyl compounds such as polyvinyl be separated by ordinary distillation methods. ethers or acetals. Thus, as described in Herr- The present invention constitutes an improvemann and Haehnel United States Patent 1,672,- I ment over the process of U. S. P. 2,109,883. An 156, a polymerized vinyl ester, such as polyvinyl object of the invention is to provide an improved l0 acetate, is.reacted in alcoholic solution with an method for partially or completely hydrolyzing alkali, such as potassium hydroxide. The prodderivatives of polyvinyl alcohol. A further obucts of the reaction are polyvinyl alcohol and an ject is to provide a method of preparing hydrolyalkaline salt of the acid corresponding to the sis products of polyvinyl alcohol derivatives polyvinyl ester used, i. e. when the initial reactwherein the degree of hydrolysis of the product 15 ants are polyvinyl acetate and potassium hydroxcan be readily and precisely controlled. A furide, polyvinyl alcohol and potassium acetate are ther object is to provide a method of hydrolyzlng formed. The principal disadvantage of this procpolyvinyl alcohol derivatives wherein the utilizan ess lies in the fact that the polyvinyl alcohol is tion of alcohols and other solvents is more ecocontaminated to a considerable extent with alkanomical than in prior methods. Other objects line salts which, as a general rule, cannot be reand advantages of the invention will be apparent moved by ordinary washing methods. Accordfrom the ensuing description thereof. ingly, in order to obtain a pure product, it is nec- In the method of the invention a polyvinyl al.- essary to resort to rather cumbersome purificacohol derivative, such as an ester, ether, acetal r tion methods, such as dissolving and reprecipior ester-acetal of polyvinyl alcohol, is reacted tating the polyvinyl alcohol or subjecting it to with an alcohol (with or without an inert diludialysis. The use of such purification methods, ent) in the presence 01 a hydrolysis catalyst, the of course, addsconsiderably to the cost of ,proproportion'of alcohol (plus inert diluent, if any) ducing the product. being such that the polyvinyl derivative is not More recently Hermann, Haehnel and Berg completely dissolved, but a plastic or doughy (U..S. P. 2,109,883) have found that polyvinyl almass is formed. I have found, very surprisingly, cohol could be obtained by the catalytic hydrolythat by mechanically working the apparently unsis of polymerized vinyl esters or other hydrolyzmanageable mass thus formed, the hydrolysis reable polymerized vinyl compounds. According to action proceeds readily and finally the mass is r this method, a solution of a polymerized vinyl converted to a slurry of the hydrolysis product, compound is reacted with an alcohol in the presfrom which the pure product may be easily sepaence of a small amount of an alkali or an acid rated. as a hydrolysis catalyst. Starting, for example, The reaction may be carried outin any of the with polymerized vinyl acetate and methanol, the conventional mixing orkneading machines such 40 products of the reaction are polyvinyl alcohol and as are commonly used in the plastic arts. The 40 methyl acetate. The amount of catalyst emmay be in the form of blade mixers, worm mixers p y i 50 Small hat no significant contaminawhich involve extruding the material through tion of the product occurs, and -it is thus possible orifices, roller mills and the like. Machines of to obtain directly polyvinyl alcohol of a high dethese types are widely used in the manufacture gree of purity without further purification. of rubber and plastics, in the. kneading of bread The foregoing method is, in most respects, very dough, etc., and therefore need not be further desatisfactory and has been extensively employed scribed for the purposes of the present invention. in the manufacture of polyvinyl alcohol. How- Preferably, the mixing machine should be proever, in carrying out this process on a commervided with cooling means, such as water coils, in cial scale, the economic recovery of the excess alorder to remove the heat generated by the hycohol and the other solvents used in, or produced drolysis reaction. by, the reaction has proven troublesome. It has As an inert solvent or diluent it is generally been considered necessary to use a considerable preferred to utilize the same ester as is formed by excess 01 alcohol in the reaction in order to disthe reaction of the alcohol with the polyvinyl essolve the polymerized vinyl ester, and it is usually ter, so that the final mother liquor contains sub- 55 lute sulfuric or hydrochloric acids. stanially only the esteror mixtures thereof with the excess alcohol used. The invention, however, is not limited to the use of such esters as solvents, as other inert solvents can be used, especially those which can be easily distilled from the reaction product, such as acetone, benzol and the like. In the process of the invention satisfactory conversion takes place readily at relatively low temperatures. It is, in fact, preferable to maintain a low temperature during the reaction period by cooling the reaction mixture. It has been found that room temperatures are especially suitable for carrying out the conversion, more particularly temperatures of about 15 to 30 C. The invention, however, is not limited to this particular temperature range since the reactions can be carried out satisfactorily at higher or lower temperatures. The hydrolysis reaction is promoted by the action of alkaline catalysts, such as sodium or potassium hydroxides, or acid catalysts, such as di- In general. alkalies are to be preferred over acids. Although pleted in the same or even less time than is required in the saponification process (in which relatively large amounts of alkalies are used), the amounts necessary are so small that they do not appreciably contaminate the reaction product. The amount of catalyst used should be substantially less than the stoichiometric equivalent of the vinyl compound. I generally prefer to utilize as a catalyst an alkali metal alcoholate of the same alcohol as is used for the hydrolysis reaction. As the hydrolyzing agent, any alcohol which is liquid under the conditions of the reaction may be used, but it has been found that methanol offers particular advantages because of the readiness with which it forms esters and because of the low boiling point of the methyl esters. However, depending upon special conditions or upon the commercial demand for the various esters formed, it may be advantageous to use other alcohols, .such as ethyl alcohol, propyl alcohol, butyl alcohol, glycols, etc. Water exerts an inhibiting effect upon the hydrolysis reaction; hence, although relatively small amounts of water may be tolerated, it is preferred that the hydrolytic alcohols, as well as the other reactants, be as nearly anhydrous as is feasible. The amount of hydrolytic alcohol used need not substantially exceed the stoichiometric equivalent of the polyvinyl .derivative being hydrolyzed in order to produce a completely hydrolyzed product. Where an only partially hydrolyzed product is desired, even less than the stoichiometric equivalent may be used. In the production of partially hydrolyzed products, the reaction may be interrupted at the desired stage of conversion by neutralizing the catalyst or by the addition of water to the reaction mixture. The following examples are given as illustrative of the invention: Example I 2100 grams of dry polyvinyl acetate (alow polymer'having a viscosity of 1'7 in a 50% solution at 20 C. as determined by the Hercules powder falling ball method) are intimately kneaded with 'a mixture of 780 grams of anhydrous methanol and -grams of anhydrous methyl acetate, containing 6.3 grams of sodium as sodium methylate. The temperature is maintained at 20 C. by water cooling. After about 20 minutes, a dough-like mass is obtained which thereafter is slowly converted into a voluminous powder. The kneading is continued for about two hours to complete alcoholysis, whereafter the formed methyl acetate is distilled off. The resultant polyvinyl alcohol is a white powder, which can be utilized for all purposes without any further treatment. The methyl acetate formed is practically pure and can be used directly for solvent purposes without further purification. Example II In a somewhat larger kneading machine than that used in Example I, 260 kg. of dry polyvinyl acetate (a high polymer having a viscosity of 40 measured as described in Example I at 20 C. but in a 20% solution) is mixed with 140 kg. of anhydrous methanol to form a homogenous mass. While maintaining the mixture at a temperature of 20 to 25 C., 250 grams of sodium, as a 1% solution of sodium methylate in methyl alcohol, are added. After 20 minutes the viscosity of the mixture increases, and the mixture then becomes voluminous and dough-like in appearance. After further kneading for 40 minutes, another 100 grams of sodium, as a 1% solution of sodium methylate in methyl alcohol, is added. The product is slowly transformed to a thick paste or slurry of polyvinyl alcohol in the mother liquor. To complete the reaction, a further amount of 150 grams of sodium in the form of a more concentrated solution of the methylate is added to the mixture. The polyvinyl alcohol is separated from this mixture as described in Example I. The resultant polyvinyl alcohol is about 99% hydrolyzed. The mixture of methyl acetate and methanol distilled off contains about 75% methyl acetate. Example I vinyl alcohol having a saponification number of about 230. It is only partially soluble in methanol and ethanol and is insoluble in water. The same result can be obtained by diluting the reaction mixture with water instead of neutralizing the catalyst with acid. Example IV Proceeding in the same way as in Example II, but neutralizing the catalyst half an hour after the second addition of sodium methylate (i. e., when the mixture contains 350 grams of sodium as sodium methylate for 260 kg. polyvinyl acetate), a product with a saponification number of about to is obtained. This product is insoluble in methanol and ethanol, but soluble in water. It is an excellent emulsifying agent. The foregoing examples describe the treatment of polyvinyl acetate; however, other polyvinyl derivatives can be similarly hydrolyzed according to the invention, as for example other esters of polyvinyl alcohol such as polyvinyl formate, propionate, and butyrate; ,also po yvinyl ethers, acetals and ester-acetals and interpolymers and mixed polymers of polyvinyl esters with each other or with other polymerizable compounds, such as the interpolymers of vinyl v esters and 'fatty oils disclosed in U. S. Patent 5 1,934,297 to Eibner et al., are suitable. The present invention affords a means of obtaining in a simple and efiicacious manner, par-' tially substituted polyvinyl alcohols of any desired degree of hydrolysis. Since the propi erties of these products vary considerably in accordance with the proportion of hydroxyl groups that remain substituted, it' is important to be able to control precisely and reproducibly the extent of hydrolysis. It is possible to do so 15 more effectively in the present process than in the methods that have been practiced heretofore. The present invention also provides a number of technical advantages which are of impor- 20 tance in the manufacture of polyvinyl alcohol. Thus, the conversion of the raw materials into the final product may be carried out in one working step and in one apparatus. The product can be dried in the reaction vessel'and no 25 filtration, extraction or other purification thereof is required. The fact that the totalamount of solvent used in the reaction is substantially less than in prior processes naturally results in lower solvent losses 30 and in important economies in the heat required for the distillation thereof. Moreover, since the process of the invention can be operated with substantially stoichiometric amounts of the hydrolytic alcohol, the by-product ester may be 35 obtained in substantially pure form, thus obviating the necessity of subjecting itto further distillation or other purification. It is to be understood that the invention is not restricted to the specific embodiments thereof 40 described hereinabove, but embraces all such variations, modifications and equivalents as fall within the scope of the appended claims. I claim: 1. The method of hydrolyzing a derivative of 45 polyvinyl alcohol which comprises reacting the same with an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mix- 50 ture being such as to form a kneadable plastic mass, and lmeading said plastic mass. 2. The method of hydrolyzing a'polymerized vinyl ester which comprises reacting the same with an alcohol which is liquid under the condi- 55 tions of reaction in the presenc'e of a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. 60 3. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis catalyst, the relative proportions of liquid and 65 solid constituents in the reaction mixture being such as to form akneadable plastic mass, and kneading said plastic mass. 4. The method of hydrolyzing a derivative of polyvinyl alcohol which comprises reacting the 7 same with methanol in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constitutents in the reaction mixture being such as to' form a kneadable plastic mass, and kneading said plastic mass. 75 5. The method of hydrolyzing poylmerized vinyl acetate which comprises reacting the same with methanol in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constitutents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. 6. The method of hydrolyzing a derivative of polyvinyl alcohol which comprises reacting the same with an alcohol which is liquid under the conditions of reaction in the presence of an alkali metal alcoholate as a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. '7. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with methanol in the presence of an alkali metal methylate as a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass', and kneading said plastic mass. 8. The method of hydrolyzing a derivative of polyvinyl alcohol which comprises reacting the same with'an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis catalyst and of an inert diluent, the ' relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. 9. The method of hydrolyzing a polymerized vinyl ester which comprises reacting the same with an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis catalyst and of an inert diluent comprising an ester corresponding to the said alcohol and the acid'residue of the said polyvinyl ester, the relative proportions of liquid and solid constituents 40 in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. 1 10. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with methanol in the presence of a hydrolysis catalyst and of methyl acetate, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass. 11. The method of hydrolyzing a polymerized vinyl ester which comprises reacting the same with an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass while maintaining the same at a temperature of 15-30 C. 12. The methodof hydrolyzing a polymerize vinyl ester which comprises reacting the same with 'an alcohol which is liquid under the conditions of reaction in the presence of a hydrolysis 1 catalyst and of an inert diluent comprising an ester corresponding to the said alcohol and the acid residue of the said polyvinyl ester, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plas-' tic mass while maintairnng the same at a temperature of 15-30 C. catalyst and of an inert diluent comprising an ester corresponding to the said alcohol and the ,acid residue of the said polyvinyl ester, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass while maintaining the same at a temperature of l-30 C. 14. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with methanol in the presence of an alkali metal methylate as a hydrolysis catalyst and of methyl acetate, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, and kneading said plastic mass while maintaining the same at a temperature of 15-30 C. 15. The method of hydrolyzing a derivative of polyvinyl alcohol which comprises reacting the same with an alcohol in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass and interrupting the reaction by neutralizing the said catalyst when the desired degree of hydrolysis has been attained. 16. The method of hydrolyzing a derivative of polyvinyl alcohol which comprises reacting the same with an alcohol in the presence of a hydrolysis catalyst, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass and interrupting the reaction by the addition of water .when the desired degree of hydrolysis has been attained. . I 17. The method of hydrolyzing a polymerized vinyl ester which comprises reacting the same with an alcohol in the presence of a hydrolysis catalyst and of an inert diluent, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass and interrupting the reaction by neutralizing the said catalyst when the desired degree of hydrolysis has been attained. 18. The method of hydrolyzing a polymerized vinyl ester which comprises reacting the same with an alcohol in the presence of a hydrolysis catalyst and of an inert diluent, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass and interrupting the. reaction by the addition of water when the desired degree of hydrolysis has been attained. 19. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with methanol in the presence of an' alkali metal methylate as a hydrolysis catalyst and of methyl acetate, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass while maintaining the same at a temperature of 15-30 C. and interrupting the reaction by neutralizing the alkali metal methylate when the desired degree of hydrolysis has been attained. 20. The method of hydrolyzing polymerized vinyl acetate which comprises reacting the same with methanolin the presence of an alkali metal methylate as a hydrolysis catalyst and of methyl acetate, the relative proportions of liquid and solid constituents in the reaction mixture being such as to form a kneadable plastic mass, kneading said plastic mass while maintaining the same at a temperature of l5-30 C., and interrupting the reaction by the addition of water when the desired degree of hydrolysis has been attained. HERBERT BERG.

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Cited By (21)

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    DE-1002527-BFebruary 14, 1957Du PontVerfahren zur Herstellung von Polyvinylalkohol
    EP-1085028-A1March 21, 2001Nippon Gohsei Kagaku Kogyo Kabushiki KaishaMethod of drying saponified ethylene-vinyl acetate copolymers
    US-2004019151-A1January 29, 2004Kuraray Co., Ltd.Method for producing saponified ethylene-vinyl acetate copolymer
    US-2007142620-A1June 21, 2007Richard Vicari, Florin Barsan, Hann Bret FMethod to purify poly(vinyl alcohol)
    US-2427126-ASeptember 09, 1947Bonard ClaudeProduction of textiles and other articles having a basis of a polyvinyl compound
    US-2430372-ANovember 04, 1947Du PontProcess for drying polyvinyl alcohol
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    US-2513488-AJuly 04, 1950Du PontMethanolysis of polyvinyl esters
    US-2915504-ADecember 01, 1959Celanese CorpPolyvinyl butyral
    US-2950271-AAugust 23, 1960Du PontAlcoholysis of polyvinyl acetate
    US-3028374-AApril 03, 1962Hoechst AgProcess for the manufacture of polyvinyl alcohol
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    US-3172876-AMarch 09, 1965Process for the manufacture of modified polyvinyl alcohols
    US-3179645-AApril 20, 1965Kurashiki Rayon CoProcess of producing polyvinyl alcohol of improved properties
    US-3365408-AJanuary 23, 1968Kurashiki Rayon CoAdhesives comprising polyvinyl alcohol bearing or mixed with substances bearing carboxyl groups, and a stabilizer
    US-4401790-AAugust 30, 1983Hoechst AktiengesellschaftProcess for the manufacture of polyvinyl alcohol by alcoholysis of a polyvinyl ester
    US-4948857-AAugust 14, 1990Air Products And Chemicals, Inc.Copolymers of vinyl acetate and acrylates
    US-6653400-B2November 25, 2003Kuraray Co., Ltd.Method for producing saponified ethylene-vinyl acetate copolymer
    US-7041731-B2May 09, 2006Kuraray Co., Ltd.Method for producing saponified ethylene-vinyl acetate copolymer
    US-7388069-B2June 17, 2008Celanese International CorporationMethod to purify poly(vinyl alcohol)