A PROCESS FOR MINIMIZING RESIDUAL FREE HYDRAZINE IN POLYMER LATICES

Abstract: This invention relates to a process for minimizing or reducing the amount of residual free hydrazine in polymer latices. The process is particularly useful in the manufacture of hydrogenated nitrile rubber which is resistant to oxidative degradation at high temperatures, as well as resistant to corrosive environments such as acid environments. Nitrile rubbers are useful in the manufacture of fan belts, seals, gaskets, and hoses in increasingly small and hot-running car engines.

Description: A PROCESS FOR MINIMIZING RESIDUAL FREE HYDRAZINE IN POLYMER LATICES Various forms of hydrogenated nitrile rubbers have recently been introduced into the marketplace. Hydrogenated nitrile rubber has the advantage of being resistant to oxidation degradation at high temperature, as well as being resistant to corrosive environments such as acid environments. These materials have found utility in the manufacture of fan belts, seals, gaskets, and hoses in increasingly small and hot-running car engines. One process for the production of hydrogenated polymers in latex form, particularly hydrogenated latex rubber, utilizes hydrazine and an unsaturated polymer as the starting materials. This process is more particularly described in U.S. Patent No. 4,452,950, assigned to the Goodyear Tire and Rubber Company. However, the product produced in accordance with the process described in the '950 patent suffers from the disadvantage of containing residual unreacted hydrazine. This residual hydrazine is considered undesirable from an environmental and/or toxicity standpoint. In view of the above, it would be highly desirable to provide a process for the elimination and/or reduction of the residual hydrazine in the polymer product mixture. In one aspect, the present invention relates to a process for reducing or eliminating hydrazine from a mixture of hydrazine and polymer, wherein said polymer is in latex form, which comprises contacting said hydrazine in said mixture with an oxygen-containing gas at an elevated pressure and a temperature of between about 20°C and about 100°C, preferably between about 20°C and about 50°C, in the presence of a hydroquinone catalyst in order to effect a reaction of said hydrazine with said oxygen-containing gas in order to produce a purified mixture containing a reduced amount of hydrazine. In another aspect, the present invention relates to a process for reducing or eliminating free hydrazine from a mixture of hydrazine and polymer, wherein said polymer is in latex form, which comprises contacting said free hydrazine in said mixture with a hydrazine scavanger in order to bind said free hydrazine, thereby reducing or eliminating the presence of free hydrazine in said latex. In yet another aspect, the present invention relates to a two-step process for reducing or eliminating hydrazine from a mixture of hydrazine and polymer, said polymer being in latex form, which comprises: (a) contacting said hydrazine in said mixture with an oxygen-containing gas at an elevated pressure and a temperature of between about 20°C and about 100°C in the presence of a quinone or hydroquinone catalyst in order to effect a reaction of said hydrazine with said oxygen-containing gas in order to produce a purified mixture containing a reduced amount of free hydrazine, and (b) contacting said free hydrazine in said purified mixture with a hydrazine scavenger in order to bind at least a portion of said free hydrazine, thereby providing a desired mixture containing a reduced amount of free hydrazine. These and other aspects of the present invention will become apparent upon a reading of the following detailed description of the invention. The catalyst useful in the present invention is a quinone or hydroquinone catalyst. The catalyst is used in a "catalytically-effective amount", i.e. an amount sufficient to catalyze the destruction of at least some of the hydrazine in the polymer/hydrazine mixture by virtue of catalysis of a hydrazine reaction with the oxygen in the oxygen-containing gas. Although the preferred hydroquinone catalyst is quinone or hydroquinone itself, derivatives of hydroquinone can be used such as alkyl (preferably lower alkyl), carboxylic acid, or sulfonyl-substituted derivatives of quinone or hydroquinone. The catalyst is employed in a catalytically- effective amount, preferably between about 0.1 and about 1 percent based upon the total weight of latex. The oxygen-containing gas employed in accordance with the process of the present invention reacts with hydrazine to produce water and nitrogen. The oxygen- containing gas is preferably air or oxygen, most preferably oxygen. The oxygen-containing gas is suitably employed in an amount of between about 100 to 300 percent excess, based on the total amount of hydrazine to be reacted. The polymer/hydrazine mixture generally contains a major amount (i.e. typically greater than 70 weight percent) of water, saturated polymer (typically about 5 to about 25 weight percent) , a minor amount of unsaturated polymer (typically between about one and five weight percent), and a minor amount (typically between about 0.1 and about 3 weight percent) of hydrazine, wherein the weight percents are based upon the total weight of the latex. For most applications, it is preferred that the amount of unsaturated polymer in the latex and the amount of hydrazine be minimized in the mixture. Reduction or elimination of the unsaturated polymer by conversion to saturated polymer is helpful in reducing the reactivity of the polymer latex. Reduction or elimination of the hydrazine in the mixture provides a mixture having reduced toxicity. The process of the present invention provides multiple advantages by both (a) reducing the amount of hydrazine in the mixture and (b) converting at least some of the unsaturated polymer to saturated polymer. The hydrazine scavenger useful in the processes of the present invention acts to bind at least some portion of the free hydrazine in the purified latex. Useful hydrazine scavengers are compounds that react with hydrazine and include the following classes of compounds: isocyanates (such as tolylene diisocyanate, phenyl isocyanate and methylene dipenyl isocyanate (MCI)); alkylene oxides (such as ethylene oxide, propylene oxide, isobutylene oxide, styrene oxide, and polymeric epoxides); acrylates and methacrylates (such as methyl methacrylate) ; acrylonitrile, acrylic acids and methacrylic acids; ketones and diketones (such as acetyl acetone); aldehydes (such as benzaldehyde) ; and combinations thereof. The preferred hydrazine scavenger is propylene oxide. The hydrazine scavenger is employed in a "scavenging effective amount". As used herein, the term "scavenging effective amount" designates an amount of hydrazine scavenger sufficient to react with and bind at least some amount of the free hydrazine in the latex mixture. Preferably, the hydrazine scavenger is employed in an amount of between about 1 and about 10, more preferably between about 1 and about 5 times the theoretical molar amount required to react with the free hydrazine present in the hydrazine/latex mixture. In a preferred embodiment of the two-step process o the present invention, step (a) of the two-step process is utilized to reduce the amount of hydrazine in the polymer/hydrazine mixture to a level of about 100 ppm or less, and then step (b) is employed to reduce the amount of free hydrazine in the mixture to 25 ppm or less. The polymer/hydrazine mixture in latex form is prepared by hydrogenation of unsaturated polymers. Prior to hydrogenation, the unsaturated polymers are typically composed of 5 to 100 percent by weight of a conjugated diene monomer unit and 95 to 0 percent by weight of an ethylenically-unsaturated monomer unit. Specific examples of the conjugated diene monomer are 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, and 1,3-pentadiene, specific examples of the ethylenically unsaturated monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile, monovinyl aromatic hydrocarbons such as styrene, (o-, m-, and p-) alkylstyrenes, divinyl aromatic such as divinylbenzene, dialkenyl aromatics such as diisopropenylbenzene, unsaturated carboxylic acids and the esters thereof such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, aleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate; vinylpyridine; and vinyl esters such as vinyl acetate. The conjugated diene polymer may be one prepared by any method of preparation, such as emulsion polymerization, solution polymerization or bulk polymerization. Specific examples of the conjugated diene polymer include polyisoprene, polybutadiene, a styrene/butadiene (random or block) copoly er, an acrylonitrile/butadiene (random or blocked) copolymer, a butadiene/isoprene copolymer, and an isoprene/isobutylene copolymer. When employing the processes of the present invention utilizing an oxygen-containing gas to remove hydrazine from the latex mixture, this step is suitably effected at an elevated pressure. The elevated pressure is preferably between about 20 and about 700 psig, more preferably between about 30 psig and about 200 psig, most preferably between about 30 psig and about 100 psig. The process is suitably effected at a temperature of between about 20°C and about 100°C, more preferably between about 20°C and about 50°C. The reaction time for the process of the present invention can vary over a wide range, but is preferably between about 1 hour and about 50 hours, more preferably between about 1 hour and about 25 hours, most preferably between about 1 hour and about 20 hours. The following examples are intended to illustrate, but in no way limit the scope of, the present invention. EXAMPLE 1 An acrylonitrile/butadiene rubber with 66.2 weight percent butadiene and an average molecular weight of about 200,000 was hydrogenated in latex form with a mixture of hydrazine and hydrogen peroxide in a manner approximately as described in Wideman, without a metal ion initiator. After achieving about 91 percent conversion of the C-C double bonds, the run was interrupted. At this point in the reaction, the latex contained 3.76 weight percent unreacted hydrazine based on the weight of the aqueous phase of the latex. This latex was placed in a pressure vessel, along with ca 0.2 weight percent hydroquinone as catalyst, the vessel flushed with pure oxygen several times and then pressured with pure oxygen to about 40 psig and allowed to react at the autogenous temperature, which generally was between 20°C and 50°C. This operation of flushing and filling the pressure reactor was repeated several times in order to provide sufficient oxygen for the reaction with hydrazine. The final hydrazine concentration after this oxygen treatment was about 100 ppm, based on the total weight of latex. The total time of treatment was about 20 hours under pressure. Comparative Example A A latex hydrogenated as described in Example 1 and hydroquinone as catalyst, were charged to a reaction flask and reacted with oxygen by bubbling the oxygen gas through - the latex at atmospheric pressure at an autogenous temperature of about 20 C C to 45°C until a large excess of oxygen had been introduced. The original concentration of hydrazine before the oxygen treatment was 3.2 percent and the level after was still 2833 ppm, based on the total weight of latex. This indicates that it is highly desirable to carry this operation out under pressure. Comparative Example B A partially hydrogenated latex was prepared as described in Example 1. When the hydrogenation step was interrupted, the latex contained about 2.4 percent hydrazine, based on the total weight of the latex. This was then subjected to a pressurized oxygen treatment as described in Example 1, except that no hydroquinone catalyst was employed. After 6.5 hours of reaction, the latex contained 2.3 percent hydrazine, indicating essentially no reaction. The run was then interrupted in order to add a catalytic amount of hydroquinone and the pressurized oxygen reaction continued for another 6.5 hours, after which the hydrazine level had been reduced to about 150 ppm. This indicates the necessity for carrying out this reaction in the presence of a catalyst such as hydroquinone. EXAMPLE 2 U.S. Patent No. 4,079,018 teaches the use of a metal complex as a catalyst for the reaction of hydrazine with oxygen. Such a complex is, for example, a cobalt-EDTA complex. When air was passed through a 34.9 percent aqueous solution of hydrazine containing this catalyst, the hydrazine level changed to 33.64 percent over a period of 2 hours. This experiment was then interrupted in order to add, as a second catalyst, a small portion of hydroquinone. Air was then bubbled through the solution at about 50°C for a period of about 7 hours, during which the hydrazine level dropped only to 32.73 percent. This indicates the desirability of using pure oxygen instead of air in order to carry out this reaction in any reasonable time under these mild conditions. EXAMPLE 3 An acrylonitrile/butadiene rubber with 66.2 weight percent butadiene and an average molecular weight of about 200,000 was hydrogenated in latex form with a mixture of hydrazine and hydrogen peroxide in a manner approximately as described in Wideman, without a metal ion initiator. After achieving about 91 percent conversion of the C-C double bonds, the run was interrupted. At this point in the reaction, the latex contained 3.76 weight percent unreacted hydrazine, based on the weight of the aqueous phase of the latex. This latex was placed in a pressure vessel, along with ca 0.2 weight percent hydroquinone as catalyst, the vessel flushed with pure oxygen several times and then pressured with pure oxygen to about 40 psig and allowed to react at the autogenous temperature, which generally was between 20 and 40°C. This operation of flushing and filling the pressure reactor was repeated several times in order to provide sufficient oxygen for the reaction with hydrazine. The final hydrazine concentration after this oxygen treatment was about 100 ppm, based on the total weight of latex. The total time of treatment was about 20 hours under pressure. To a portion of the above latex, a molar excess of toluene diisocyanate (TDI) (relative to the hydrazine present) was added at room temperature and stirred for two hours. The final free hydrazine content was about 50 ppm, based on the total weight of the latex. EXAMPLE 4 To another portion of the hydrogenated latex as prepared in Example 3, an excess of propylene oxide was added at room temperature and stirred for two hours. Again the final free hydrazine content was about 50 ppm, based on the total weight of the latex. EXAMPLE 5 A latex sample was prepared substantially as per Example 3, up to and including the pressurized oxygen step. The conversion of the C=C bonds was about 90 percent complete at the end of the reaction and the hydrazine level in the aqueous phase of the latex was treated with an excess of propylene oxide, stirred for one hour at room temperature and then for an additional hour at 80-85°C. The final level of free hydrazine in the aqueous phase of the latex was 17 ppm hydrazine. EXAMPLE 6 An acrylonitrile/butadiene rubber with 66.2 weight percent butadiene and an average molecular weight of about 200,000 was hydrogenated in latex form with a mixture of hydrazine and hydrogen peroxide in a manner approximately as described in Wideman, without a metal ion initiator. After achieving about 88 percent conversion of the C=C double bonds, the run was interrupted. At this point in the reaction, the latex contained 4.05 weight percent unreacted hydrazine, based on the weight of the aqueous phase of the latex. To a portion of this hydrogenated latex was added an excess of methyl acrylate and stirred at room temperature for 1.5 hours. During this period, there was a noticeable exotherm. The final hydrazine content was about 4.73 ppm, based on the weight of the aqueous phase of the latex, which represents about a 99 percent removal of hydrazine from the latex. The above Examples and Comparative Examples demonstrate the desirability of removing residual hydrazine from a hydrogenated rubber latex by reacting the latex under mild thermal conditions in a process that involves all of the following: a catalyst, essentially pure oxygen or air enriched in oxygen, and elevated pressures.

Claims: WHAT IS CLAIMED IS: 1. A process for reducing or eliminating hydrazine from a mixture of hydrazine and polymer, wherein said polymer is in latex form, characterized by contacting said hydrazine in said mixture with an oxygen-containing gas at an elevated pressure and a temperature of between about 20°C and about 100°C in the presence of a quinone or hydroquinone catalyst in order to effect a reaction of said hydrazine with said oxygen-containing gas in order to produce a purified mixture containing a reduced amount of hydrazine. 2. The process of claim 1 characterized in that said pressure is between about 20 and about 700 psig. 3. The process of claim 1 characterized in that said pressure is between about 30 psig and about 200 psig. 4. The process of claim 1 characterized in that said pressure is between about 30 psig and about 100 psig. 5. The process of claim 1 characterized in that said temperature is between about 20°C and about 100°C. 6. The process of claim 1 characterized in that said temperature is between about 20°C and about 50°C. 7. The process of claim 1 characterized in that said reaction is conducted for a reaction time of between about 1 hour and about 50 hours. 8. The process of claim 1 characterized in that said reaction is conducted for a reaction time of between about 1 hour and about 25 hours. 9. The process of claim 1 characterized in that said reaction is conducted for a reaction time of between about 1 hour about 20 hours. 10. The process of claim 1 characterized in that said oxygen-containing gas is pure oxygen, or air, or a combination thereof. 11. A process for reducing or eliminating free hydrazine from a mixture of hydrazine and polymer, characterized in that said polymer is in latex form, characterized by contacting said free hydrazine in said mixture with a hydrazine scavenger in order to bind said free hydrazine, thereby reducing or eliminating the presence of free hydrazine in said latex. 12. The process of claim 11 characterized in that said hydrazine scavenger is employed in a scavenging effective amount. 13. The process of claim 11 characterized in that said hydrazine scavenger is employed in an amount of between 1 and 10 times the theoretical molar amount required to react the free hydrazine present in said mixture. 14. The process of claim 11 characterized in that said hydrazine scavenger is selected from the group consisting of isocyanates, alkylene oxides, acrylates, methacrylates, acrylic acids, acrylonitrile, methacrylic acids, ketones, diketones, aldehydes, and combinations thereof. 15. The process of claim 11 characterized in that the hydrazine scavenger is propylene oxide. 16. A two-step process for reducing or eliminating hydrazine from a mixture of hydrazine and polymer, said polymer being in latex form, characterized by: (a) contacting said hydrazine in said mixture with 5 an oxygen-containing gas at an elevated pressure and a temperature of between about 20°C and about 100°C in the presence of a quinone or hydroquinone catalyst in order to effect a reaction of said hydrazine with said oxygen-containing gas in order ig to produce a purified mixture containing a reduced amount of free hydrazine, and (b) contacting said free hydrazine in said purified mixture with a hydrazine scavenger in order to bind at least a portion of said free hydrazine, thereby 15 providing a desired mixture containing a reduced amount of free hydrazine therein. 17. The process of claim 16 characterized in that said hydrazine scavenger is employed in a scavenging effective amount. 18. The process of claim 16 characterized in that said hydrazine scavenger is employed in an amount of between 1 and 10 times the number of moles of hydrazine present in said mixture. 19. The process of claim 16 characterized in that said hydrazine scavenger is selected from the group consisting of isocyanates, alkylene oxides, acrylates, methacrylates, acrylic acids, acrylonitrile, methacrylic 5 acids, ketones, diketones, aldehydes, and combinations thereof. 20. The process of claim 16 characterized in that the hydrazine scavenger is propylene oxide. 21. The process of claim 16 characterized in that said pressure is between about 20 and about 700 psig. 22. The process of claim 16 characterized in that said pressure is between about 30 psig and about 200 psig. 23. The process of claim 16 characterized in that said pressure is between about 30 psig and about 100 psig. 24. The process of claim 16 characterized in that said temperature is between about 20°C and about 100°C. 25. The process of claim 16 characterized in that said temperature is between about 20°C and about 50°C. 26. The process of claim 16 characterized in that said reaction is conducted for a reaction time of between about 1 hour and about 50 hours.

Inventors: MANKE STEVEN A, SCHIESSL HENRY W, MANKE, STEVEN, A., SCHIESSL, HENRY, W.
Applicants: OLIN CORP, OLIN CORPORATION
Application year: 1990
Main classification: C08F6
IPC codes: C08C1, C08C19, C08F6, C08F8