The method of obtaining ammonium salt polyamide copolymer of maleic anhydride and styrene glycol recoletos

 

(57) Abstract:

The invention relates to methods of producing cross-linked copolymers of maleic anhydride with styrene, in particular the production of ammonium salts polyamide copolymer of maleic anhydride and styrene, Recoletos ethylene glycol, which is used to obtain formulations of pesticides, as well as cosmetic, pharmaceutical and veterinary products. The method consists in the interaction of maleic anhydride with styrene in the presence of the initiator is benzoyl peroxide blended formed of the copolymer of the ethylene and the copolymerization and the stitching of the resulting copolymer is carried out in one stage, downloading simultaneously into the reactor maleic anhydride, styrene, ethylene glycol and benzoyl peroxide in a molar ratio of ethylene to maleic anhydride 0,03 - 0,10 : 1 with subsequent treatment of the obtained cross-linked copolymer with gaseous ammonia. The method allows to obtain the ammonium salt of polyamide copolymer of maleic anhydride and styrene, Recoletos glycol, capable of forming aqueous gels with a given viscosity necessary for preparation of the gel preparative forms.

The invention from what Monini salt polyamide copolymer of maleic anhydride and styrene, Recoletos ethylene glycol, which is used as a gelling to obtain formulations of pesticides, as well as cosmetic, pharmaceutical and veterinary products.

A method of obtaining cross-linked copolymers of unsaturated dicarboxylic acid in anhydrous form, in particular maleic anhydride with styrene or-methylstyrene, where as cross-linking agents using an aromatic polyfunctional amines, polyols and other (U.S. patent N 4435383).

The method is carried out in two stages: first, carry out the copolymerization of these monomers, and then spend the stitching of the obtained copolymer cross-linking agent.

These cross-linked copolymers used for the preparation of pesticidal compositions. However, the resulting copolymers do not form gels in water and are used in pesticide compositions in the form of wettable powders, granules or strips.

There is also known a method of obtaining a cross-linked copolymers interaction of maleic anhydride with styrene using as a crosslinking agent of the alkali metal glycolate (ed. St. USSR N 202520).

The method is carried out in two stages. In the first stage, carry out the copolymerization maleinated are blended copolymer selected by glycolate, potassium at a molar ratio of glycolate, potassium to maleic anhydride is 0.5:1.

The resulting cross-linked copolymers are able to absorb and retain in a gelatinous state to 99.5-99.6% of water, keeping the original solid sample, but not soluble either in water or in organic solvents. However, they are not capable of forming gels with water with a given viscosity necessary for preparation of the gel preparative forms.

It is established that this requirement meets the ammonium salt of polyamide copolymer of maleic anhydride and styrene, Recoletos glycol. However, this substance and its production method is not described in the literature.

The task of the invention is to develop a method of producing ammonium salts polyamide copolymer of maleic anhydride with styrene, Recoletos glycol, capable of forming aqueous gels with a given viscosity necessary for preparation of the gel preparative forms.

The method consists in the interaction of maleic anhydride with styrene in the presence of the initiator benzoyl peroxide blended formed of a copolymer of ethylene glycol at a temperature of 70-75oC for 4-5 hours, and the copolymerization and the stitching of the resulting copolymer is carried out in one stage, loading is compared linking agent ethylene to maleic anhydride is 0.03 - 0,10 : 1.

The temperature was then reduced to 20-25oC and miss gaseous ammonia within 2-3 hours. The resulting suspension is filtered, the precipitate washed on the filter with acetone and dried at a temperature of 60oC. to produce a powder of white or slightly yellow, which represents an ammonium salt polyamide copolymer of maleic anhydride and styrene, Recoletos glycol. The resulting powder was characterized by very high hygroscopicity. The elemental composition due to sorption of water may vary within a wide range and can be characterized by absolute dry substance. For a copolymer of such a structure concepts such as molecular weight, molecular weight distribution, degree of polymerization - physical. Therefore, to produce such indicators is not possible.

Water gel-like solutions of the obtained copolymer are related to non-Newtonian fluids, the viscosity of which depends on dynamic parameters of the measuring system. For quality control of the obtained copolymer used indicator is the apparent dynamic viscosity of 1% aqueous solution of the copolymer at 20oC and shear rate 500-1that should the situation in water at a concentration of 1-5% forms stable gels, which can be used to prepare gel preparative forms.

It should be noted that the importance for the implementation of the tasks is of the order of the reaction: simultaneous loading of participating in polymerization and blending agents with subsequent processing of the obtained cross-linked copolymer of ammonia.

It should also be noted that to obtain the target copolymer, which had the properties of a gel, significant is the amount of crosslinking agent ethylene glycol, which take 0,03-0,10 mol per 1 mol of maleic anhydride (unlike the proposed method, the number of cross-linking agent, for example, one of the analogs - ed. St. USSR N 202520 is 0.5 mol per 1 mol of maleic anhydride, which is 5 times higher than in the claimed method).

When used in the reaction of ethylene glycol < 0,03 mol per 1 mol of maleic anhydride target cross-linked copolymer forms a low-viscosity gels with water (viscosity of < 90 mPas), with ethylene glycol in excess of 0.1 mole, a solid bad swelling or completely nanabhai in water product, to obtain from it a gel-like form is impossible.

Also the blowing processing of the obtained cross-linked copolymer of gaseous ammonia to the disclosure anhydrite links with the formation of ammonium salts polyamide copolymer of maleic anhydride and styrene, Recoletos glycol.

If ammonia does not hold, the resulting cross-linked copolymer also will not possess the properties of a gel, this will produce a slurry of polymer in water.

It should also be noted that if the treatment with ammonia is carried out simultaneously with the stage of the polymerization and crosslinking, the resulting formed product, soluble in water.

The polymerization in this case almost never occurs because the maleic anhydride reacts with ammonia to disclosure anhydrite groups with obtaining a product, much less active in the polymerization, than actually maleic anhydride.

Example 1. Charged to the reactor a solution of 9.8 g (0.1 mole) of maleic anhydride in 100 ml of benzene, of 10.4 g (0.1 mole) freshly styrene, 0,38 g (0,006 mole) of ethylene glycol and 0.20 g of benzoyl peroxide (1% of the total mass of monomers), heated to 70oC under stirring, maintaining the temperature of the reaction mass 70-75oC for 4-5 hours until the end of the polymerization process, which is judged by the temperature reduction at the completion of the exothermic reaction, after which withstand the reaction mass within 1 chaut gaseous ammonia within 2-3 hours. The reaction of interaction with ammonia is also exothermic, the end of the process is judged to reduce the temperature of the reaction mass.

The resulting suspension is filtered, the precipitate washed on the filter with acetone, dried at a temperature of 60oC to constant weight. Get the powder white or slightly yellowish color. For quality control prepare a 1% aqueous solution of the obtained polymer, which is a gel, and determine the apparent dynamic viscosity at 20oC and shear rate 500-1on the viscometer "Polymer RPE-1M.1, which is 146 mPas.

Example 2. Carried out analogously to example 1, except the amount of cross-linking agent ethylene glycol, which take 0.18 g (of 0.003 mol). Apparent dynamic viscosity of 1% aqueous solution of the obtained copolymer, which is a gel at 20oC and shear rate 500-190 mPas.

Example 3. Carried out analogously to example 1, except the amount of cross-linking agent ethylene glycol, which we take to 0.62 g (0,01 mol). Apparent dynamic viscosity of 1% aqueous solution of the obtained copolymer, which is a gel at 20oC and shear rate 500-1SOS is a cross-linking agent, ethylene glycol, whom 0.12 g (0,002 mol). The resulting copolymer when dissolved in water forms a low-viscosity gel. Apparent dynamic viscosity of 1% aqueous solution of the copolymer at 20oC and shear rate 500-1is 28 mPas that makes it impossible to use it for cooking preparative forms.

Example 5 (comparative). Carried out analogously to example 1, except the amount of cross-linking agent ethylene glycol, which take 9.3 g (0.15 moles). The resulting copolymer is not soluble in water.

Example 6 (comparative). Carried out analogously to example 1, except that polymerization of maleic anhydride and styrene and the stitching of the resulting copolymer with ethylene glycol is carried out in two stages, loading on the first stage copolymerization into the reactor a solution of 9.8 g (0.1 mole) of maleic anhydride in 100 ml of benzene, of 10.4 g (0.1 mole) freshly styrene and 0.20 g of benzoyl peroxide (1% of the total mass of monomers). Stand under stirring for 4-5 hours at a temperature of 70-75oC and 1 hour at 80oC. To the resulting suspension of the copolymer in benzene type of 0.38 g (0,006 mole) of ethylene glycol and stirred at 70-75oC for 2 hours. After treatment of the reaction mass ammonia is polyamide copolymer of maleic anhydride and styrene, Recoletos glycol, characterized in that the copolymerization and the stitching of the resulting copolymer is carried out in one stage, downloading simultaneously into the reactor maleic anhydride, styrene, crosslinking agent is ethylene glycol and the initiator is benzoyl peroxide at a molar ratio of ethylene to maleic anhydride 0,03-0,10:1 with subsequent treatment of the obtained cross-linked copolymer with gaseous ammonia.

 

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