Acrylic filming agent production process

FIELD: polymer production.

SUBSTANCE: invention relates to processes of producing lacquer acrylic filming agents used in manufacture of masonry, road-line, and other paints. Process of invention is realized by two-step polymerization of butyl acrylate, methyl methacrylate, styrene, and methacrylic acid at ratio (40-5):(40-45):(10-14):(1-5) in toluene-ethyl acetate mixture, while portionwise feeding monomers/initiator mixture and repeatedly ageing reaction mixture. When conversion of monomers attains 82-85%, solution of butyl acrylate/styrene/methacrylic acid copolymer is additionally charged at ratio 42:57:1 dissolved in toluene/butanol (or ethanol) mixture or toluene/acetone mixture, or in toluene/ethyl acetate/ethanol/butanol mixture. Butyl acrylate/styrene/methacrylic acid copolymer is added in amount 1.77-4.0% based on concentration of principal substance. Toluene and ethyl acetate are used in proportion (0.1-1.0):1. In the first stage, 20-30% of butyl acrylate/methyl methacrylate/styrene/methacrylic acid mixture is added and, in the second stage, 70-90%. Thus obtained filming agent is characterized by high content of nonvolatile substances at rather low viscosity, high adhesion, good strength and film drying rate, low moisture absorption, high water and wear resistance.

EFFECT: improved performance characteristics of agent.

9 cl, 4 tbl, 7 ex

 

The invention relates to methods of producing acrylic lacquer film-forming agents, which are used in the production of exterior, road marking and other colors.

Known methods for producing acrylic binders in organic solvents in the presence of radical initiators of the type in which the components of the reaction mixture is served a La carte and as solvents used aromatic hydrocarbons, aliphatic esters of diatomic alcohols.

The known method of polymerization of the acrylate in toluene, which is heated to 95°With the solvent for 4 hours enter acrylate with dissolved initiator (benzoyl peroxide). At the end of the dosing impose additional benzoyl peroxide and the mixture is maintained at a temperature synthesis of 2 hours. At 40%solids content of the polymer in solution, the product has a viscosity of 55 centipoise at 30°C. (Marek O., Momka. Acrylic polymers. M-L, "Chemistry", 1966, p.84).

The described method produces a polymer having a sufficiently high molecular weight, a satisfactory viscosity, but does not guarantee the whole set of properties required for the foaming agent used in paints for road marking. Thus, high molecular weight of the obtained polymer, ensuring a high cohesive features the properties of the coating, does not provide the necessary adhesion to the surface and reduces lacquer compatibility with the components of the paint. Toluene used as the sole solvent, does not provide fast drying film and unsafe from an environmental point of view.

A known method of producing a copolymer of methyl and butyl methacrylate with dimethylphenylcarbinol providing for the supply of part of the mixture of monomers and solvent (ethyl cellosolve) dissolved therein an initiator (benzoyl peroxide) in the reactor, with him the other part of the mixture of monomers and solvent. The copolymerization process are for 8 hours at a temperature 87-92°C. (Zebrowski CENTURY Technology of synthetic resins used for the production of varnishes and paints. M., "Higher school", 1968, str-113).

The way to obtain this copolymer has a number of advantages: simple instrumentation, the short duration of the synthesis of sufficient simplicity of the process. In this method of polymerization, the resulting copolymer is characterized by a high uniformity of the molecular weight, a good reproducibility of performance properties. However, the process at high temperature results in a polymer with a high degree of branching, which gives an increased viscosity of the resulting lacquer and higher the relative stiffness of the film. Use as solvent of ethyl cellosolve, characterized by a large molar volume and high boiling point, can ensure quick drying. In addition, the high content of residual ethyl cellosolve in the film reduces the resistance of the coating.

The closest technical solution is the method of producing a copolymer of acrylic monomers with vinylaromatic connection. The method of copolymerization is carried out in two stages as follows. The monomers are mixed and 20 parts of this mixture are added 10 parts of xylene. When the temperature reached 100°injected With 0.2 parts of Quaternary butylperbenzoate dissolved in 1 part of xylene. 10 minutes after reaching 100°C for 2.5 hours to evenly dispense 80 parts of the Monomeric mixture and 1.8 parts of Quaternary butylperbenzoate dissolved in 9 parts of xylene. Then the reaction mass is allowed to stand for 1 hour at a temperature of 100°C. Further distilled residual monomers in vacuum. The obtained copolymer was dissolved in isopropyl alcohol, neutralized and diluted with water. As monomers used in addition to styrene, esters of acrylic or methacrylic acid, acrylic or methacrylic acid. (Application No. 3022824, Germany. Appl. 19.06.80, publ. 7.01.82 IPC C 08 F 212/00).

The resulting foaming agent has Neva is Oka mass fraction of non-volatiles, high viscosity, low adhesion and cohesion characteristics of the film, long drying time and low hardness and water resistance.

The present invention is to obtain a film-forming agent, combining the necessary physico-chemical properties of the film, which provide high performance paint.

The technical result of the invention is the relatively low viscosity of the foaming agent with high content mass fraction of non-volatiles, maximum adhesion, high abrasion resistance, excellent water resistance, low drying time of the film.

A new method for producing a film-forming agent includes a two-stage copolymerization in the medium of organic solvent in the presence of a radical initiator type in portions of the filing of the components of the reaction mixture and adding a solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1.

As monomers for the synthesis of the basic copolymer used butyl acrylate, methyl methacrylate, styrene and methacrylic acid, taken in the ratio (40-45):(40-45):(10-14):(1-5). As the organic solvent a mixture of toluene and ethyl acetate, taken in the ratio of 0.1-1):1. The ratio of monomers and solvents extending t is (1-2):1.

As initiator using azodiisobutyronitrile in the amount of 2-5% by weight of monomers.

Charged to the reactor toluene in the amount of 89-97% of its mass and the ethyl acetate in the amount of 9-90% of its mass. The first portion of the initiator, comprising 2-5% of its total mass is dissolved in the first portion of the mixture of monomers comprising 10-30% of its total mass, and loaded into the reactor. The reaction mass is heated to 78-80°and maintain its 1.5 hours.

The second portion of initiator in the amount of 15-20% of its total mass dissolved in a mixture of solvents containing from 1.0 to 3.0% by weight of toluene and 10-13% by weight of ethyl acetate, and served in the reactor. The reaction mass is incubated for 30 minutes at a temperature of synthesis.

The second portion of the mixture of monomers in an amount of 70-90% of its mass is metered in over 5 hours or dissolved in the 3rd portion of the initiator, which is 75-83% of its mass, or the second portion of the mixture of monomers is metered in parallel with the solution of the third portion of the initiator, dissolved in a mixture of toluene and ethyl acetate, taken in a ratio of 8.5:(52-55). At the end of the dosing of the components of the reaction mass is again incubated 1.5 hours at a temperature of synthesis.

Upon reaching a conversion of the monomers 82-85% additionally introduced into the reactor copolymer of butyl acrylate, styrene and methacrylic acid in the form of a solution with a concentration of 8-16,5 wt.% in a mixture of tolua the a and butanol, taken in the ratio 1:1, or toluene and ethanol, taken in the ratio 1:1, or toluene, ethanol and butanol, taken in the ratio of 1:0,5:0,5, or toluene and acetone, taken in the ratio 1:1, or toluene, ethyl acetate, ethanol and butanol, taken in the ratio 1:3:2:2. Copolymer of butyl acrylate, styrene and methacrylic acid is administered in the amount of 1,77-4.0 wt.%, calculated from the concentration of the basic copolymer. The reaction mass is allowed to stand for 1 hour at a temperature of synthesis.

Copolymer of butyl acrylate, styrene and methacrylic acid get by any known method, including the method of emulsion polymerization followed by selecting it in powder form.

Distinctive features of the new method are obtaining a copolymer of butyl acrylate, methyl methacrylate, styrene and methacrylic acid in a ratio (40-45):(40-45):(10-14):(1-5) in the environment of toluene and ethyl acetate, the rationed supply of the mixture of monomers and initiator, multiple exposure of the reaction mixture and adding a solution of a copolymer of butyl acrylate, styrene and methacrylic acid, with a ratio of 42:57:1 mixture of toluene and butanol or ethanol, or toluene and acetone, or toluene, ethyl acetate, ethanol and butanol. All the hallmarks are new.

It can be assumed that the required performance properties of the film are achieved midrange is t, that the resulting copolymer is a mixture of copolymers of various molecular weights, obtained at different stages of copolymerization and having different physico-chemical and physico-mechanical properties.

The copolymer obtained in the 1st stage copolymerization due to the described techniques, has a higher molecular weight that provides good cohesion, abrasion resistance and other strength characteristics of the film.

The copolymer obtained in stage 2, provides high adhesion, low viscosity, due to its lower molecular weight.

The introduction of additional solution of the copolymer leads to a decrease in the viscosity of the foaming agent while maintaining the high content mass fraction of non-volatiles, as well as to improve the strength characteristics of the film due to its high molecular weight.

The combination of copolymers of various molecular weights, and use in the synthesis solvent, characterized by a relatively small molar volume and high volatility, contributes to the formation of such patterns of foaming agent, which provides fast removal of the solvent, which leads to a significant reduction in the drying time of the film.

As a result of implementation of the new fashion obtained plait is a film binder, which is characterized by a high content of non-volatiles (42,9-61,5%) at a sufficiently low viscosity (16-220 with VZ-246 nozzle 4), high adhesion (1 point), good hardness of the film (from 0.3 to 0.44$), fast drying time (20-35 minutes), low moisture absorption (0,2-0,3%), very good water resistance (over 400 hours), high resistance to abrasion (more than 20 kg/μm without changes).

The invention is illustrated by the examples.

Example 1

Charged to the reactor, wt.%: 17 (89% of the total weight) of toluene, 2 (32% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 15% of the total weight of the mixture of monomers.

The first portion of the mixture of monomers comprises, by wt.%: 2.5 butyl acrylate, 2.9 methacrylate, 0.9 styrene and 0.16 methacrylic acid. The ratio of monomers is 40:45:12,5:2,5. Previously in the first portion of the monomers is dissolved first portion of azodiisobutyronitrile in an amount of 0.1 wt.%, what is 5% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile in the number 0,384 wt.%, that is 20% of the total weight of the initiator.

The second portion of the initiator is a pre-prepared solution in a mixture of solvents, sod is Rashi, wt.%: 0,381 azodiisobutyronitrile, 0,48 (2.5% of total weight) of toluene, 2,9 (13% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes at a temperature of synthesis.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours parallel to dispense a second portion of the mixture of monomers and a third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 85% of the total weight of the monomers and includes, in wt.%: 14.5 butyl acrylate, 16.5 methyl methacrylate, 4.5 styrene, 0,91 methacrylic acid. The ratio of monomers is 40:45:12,5:2,5.

The third portion of azodiisobutyronitrile is 75% of the total mass of the initiator. It is a pre-prepared solution comprising, by wt.%: 1.44 azodiisobutyronitrile, 1.6 toluene and 12.3 ethyl acetate. The ratio of toluene and ethyl acetate is 8,5:55. At the end of the dosing spend the shutter speed for 1.5 hours at a temperature of synthesis.

The ratio of toluene and ethyl acetate at the end of the 2nd stage copolymerization is 1:1. The ratio of the mixture of monomers to the solvent mixture is 1:1.

Upon reaching a conversion of 82% in the reaction mass enter the 8%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken with a ratio of 42:57:1 in a mixture of toluene, utilized is the butanol and ethanol, taken in the ratio 1:3:2:2. The amount of copolymer is 2 wt.% from the calculated concentration of the basic copolymer at the end of the 2nd stage copolymerization. After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour at a temperature of synthesis, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Example 2

Charged to the reactor, wt.%: (Jn 19 : 26 (97% of the total weight) of toluene, 20,8 (90% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 10% of the total weight of the mixture of monomers.

The first portion of the mixture of monomers comprises, by wt.%: 1.7 butyl acrylate, 1.7 methacrylate, 0.6 styrene and 0.04 methacrylic acid. The ratio of monomers is 42,5:42,5:14:1. Previously in the first portion of the monomers is dissolved first portion of azodiisobutyronitrile in the amount of 0.04 wt.%, that is 2% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile in the amount of 0.29 wt.%, that is 15 wt.% from the whole mass of the initiator. The second portion of the initiator is a pre-prepared solution in a mixture, R is Stroiteley, containing, wt.%: 0.29 azodiisobutyronitrile, 0,6 (3% of the total weight) of toluene, 2,3 (10% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes at a temperature of synthesis.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours to dispense a second portion of the mixture of monomers with a pre-dissolved in a third portion of azodiisobutyronitrile in the number 1,58 wt.%, that is 83% of the total mass of the initiator. The second portion of the mixture of monomers is 90% of the total weight of the monomers and includes, in wt.%: 15.3 butyl acrylate, 15.4 methacrylate, 5.0 styrene, 0,34 methacrylic acid. The ratio of monomers is 42,5:42,5:14:1. At the end of dosing are aging at a temperature of synthesis for 1.5 hours. The ratio of toluene and ethyl acetate at the end of the second stage copolymerization is 0.9:1. The ratio of the mixture of monomers to the solvent mixture is 0.93:1.

Upon reaching a conversion of 83% in the reaction mass is injected 13%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken with a ratio of 42:57:1 mixture of toluene, butanol and ethanol, taken in the ratio of 1:0,5:0,5. The amount of copolymer is 4% of the calculated concentration of the basic copolymer at the end of the second stage copolymerization. After in the edenia solution additional copolymer reaction mass is maintained at a temperature synthesis of 1 hour, then the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Example 3

Charged to the reactor, wt.%: 12 (90,5% of the total weight) of toluene, and 5.5 (35% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 20% of the total weight of the monomers.

The first portion of the mixture of monomers comprises, by wt.%: 5.3 butyl acrylate, 4.7 methacrylate, 1.16 styrene and 0,58 methacrylic acid. The ratio of monomers is: 45:40:10:5.

Previously in the first portion of the monomers is dissolved first portion of azodiisobutyronitrile in the amount of a 0.035 wt.%, that is 2% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile, comprising 20% of the total weight of the initiator. The second portion of the initiator is a pre-prepared solution in a solvent mixture containing, wt.%: 0.35 azodiisobutyronitrile, 0,13 (1% of total weight) toluene, 2 (13% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes.

In the second stage copolymerization into the reactor at a temperature of 78-80°C for 5 hours parallel to dispense a second portion with the art of the monomers and the third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 80% of the total weight of the monomers and includes, in wt.%: 21.2 butyl acrylate, 18.8 methacrylate, with 4.64 styrene, 2,32 methacrylic acid. The ratio of monomers is 45:40:10:5.

The third portion of azodiisobutyronitrile is a pre-prepared solution comprising, by wt.%: 1.37 azodiisobutyronitrile, 1.13 toluene, 8,1 ethyl acetate. The ratio of toluene and ethyl acetate equal to 8.5:52.

At the end of dosing are aging at a temperature of synthesis for 1.5 hours. The ratio of toluene and ethyl acetate at the end of the second stage copolymerization is 0.9:1, the ratio of the mixture of monomers to the solvent mixture is 2:1.

Upon reaching a conversion of 84% in the reaction mass is injected 16,6%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1 mixture of toluene and acetone, taken in the ratio 1:1. The amount of copolymer is 2,63 wt.% from the calculated concentration of the basic copolymer at the end of the second stage copolymerization. After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour at a temperature of synthesis, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Example 4.

Charged to the reactor, wt.%: 15,45 (89, of the total weight) of toluene, 7,6 (37% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 30% of the total weight of the mixture of monomers.

The first portion of the mixture of monomers comprises, by wt.%: 6.6 butyl acrylate, 5.9 methyl methacrylate, 1.5 styrene, 0.75, and methacrylic acid. The ratio of monomers in this case is 45:40:10:5. Previously in the first portion of the monomers is dissolved first portion of azodiisobutyronitrile in the amount of 0.03 wt.%, that is 3% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile, comprising 17% of the total weight of the initiator. The second portion of the initiator is a pre-prepared solution comprising, by wt.%: 0.17 azodiisobutyronitrile, 0,35 (2% of the total weight) of toluene, and 2.0 (10% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours parallel to dispense a second portion of the mixture of monomers and a third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 70% of the total weight of the monomers and includes, in wt.%: 15.4 butyl acrylate, 13.7 methacrylate, 3,4 styrene and 1.75 methacrylic KIS is the notes. The ratio of monomers is 45:40:10:5. The third portion of azodiisobutyronitrile is 80 wt.% from the total mass of the initiator and is a pre-prepared solution comprising, by wt.%: 0.8 azodiisobutyronitrile, 1.5 toluene, 10.6 ethyl acetate. The ratio of toluene and ethyl acetate equal to 8.5:53.

At the end of the dosing spend the shutter speed for 1.5 hours at a temperature of synthesis. The ratio of toluene and ethyl acetate at the end of the 2nd stage copolymerization is 0.9:1, the ratio of the mixture of monomers to the solvent mixture is 1.3:1.

Upon reaching a conversion of 85% in the reaction mass enter the 8%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1 mixture of toluene and butanol, taken in the ratio 1:1. The amount of copolymer is 1,78% of the calculated concentration of the copolymer at the end of the 2nd stage copolymerization.

After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour at a temperature of synthesis, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Example 5

Charged to the reactor, wt.%: 18,8 (89% of the total weight) of toluene, and 0.8 (32% of the total mass of ethyl acetate) and the first portion of the mixture of monomers constituting 15% of the total weight of the mixture of mono is'.

The first portion of the mixture of monomers comprises, by wt.%: 2.9 butyl acrylate, 2.6 methacrylate, 0.6 styrene and 0.15 methacrylic acid. The ratio of monomers in this case is 45:40:10:5.

Previously in the first portion of the monomers is dissolved first portion of azodiisobutyronitrile in the amount of 0.15 wt.%, what is 5% of the total weight of azodiisobutyronitrile.

Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile, comprising 20% of the total weight of the initiator. The second portion of the initiator is a pre-prepared solution in a solvent mixture containing, wt.%: 0.38 azodiisobutyronitrile, of 0.5 (2.5% of the total weight) of toluene and 2.7 (13% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes at a temperature of synthesis.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours parallel to dispense a second portion of the mixture of monomers and a third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 85% of the total weight of the monomers and includes, in wt.%: 16.5 butyl acrylate, 14.7 methacrylate, 3.7 styrene, or 0.83 methacrylic acid. The ratio of monomers is 45:40:10:5.

The third is the portion of azodiisobutyronitrile is 75% of the total mass of the initiator. It is a pre-prepared solution comprising, by wt.%: 1.42 azodiisobutyronitrile, 1.7 toluene, 11.5 ethyl acetate. The ratio of toluene and ethyl acetate is 8,5:53.

At the end of dosing are aging at a temperature of synthesis for 1.5 hours. The ratio of toluene and ethyl acetate at the end of the second stage copolymerization is 1:1, the ratio of the mixture of monomers to the solvent mixture is 1:1.

Upon reaching a conversion of 83% in the reaction mass enter the 8%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1 mixture of toluene and ethanol, taken in the ratio 1:1. The amount of copolymer is 2.2% of the calculated concentration of the copolymer at the end of the second stage copolymerization.

After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour at a temperature of synthesis, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Example 6

Charged to the reactor, wt.%: 9,17 (89% of the total weight) of toluene, 6,7 (32% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 15% of the total weight of the mixture of monomers.

The first portion of the mixture of monomers comprises, by wt.%: 3.8 butyl acrylate, 3,4 methacrylate, 0.8 styrene and 0.4 m is acrylaway acid. The ratio of monomers in this case is 45:40:10:5.

Previously in the first portion of the mixture of monomers is dissolved first portion of azodiisobutyronitrile in number with 0.125 wt.%, what is 5% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile, comprising 20% of the total weight of the initiator. The second portion of the initiator is a pre-prepared solution in a solvent mixture containing, wt.%: 0.5 azodiisobutyronitrile, 0,26 (2.5% of total weight) toluene, 2,6 (13% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes at a temperature of synthesis.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours parallel to dispense a second portion of the mixture of monomers and a third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 85% of the total weight of the monomers and includes, in wt.%: 21.3 butyl acrylate, 18.9 methacrylate, 4.8 styrene, 2,4 methacrylic acid. The ratio of monomers is 45:40:10:5.

The third portion of azodiisobutyronitrile is 75% of the total mass of the initiator and is a pre-sentence on blenny solution includes wt.%: 1.88 azodiisobutyronitrile, 0.87 toluene and 11.3 ethyl acetate.

At the end of the dosing spend the shutter speed for 1.5 hours. The ratio of toluene and ethyl acetate at the end of the second stage copolymerization is 0.5:1. The ratio of the mixture of monomers to the solvent mixture is 1.8:1.

Upon reaching a conversion of 82% in the reaction mass is injected 13,2%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1 in a mixture of toluene, butanol and ethanol, taken in the ratio of 1:0,5:0,5. The amount of copolymer is of 2.26% of the nominal concentration of copolymer in the reaction mass at the end of the 2nd stage copolymerization. After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 4.

Example 7

Charged to the reactor, wt.%: 3,1 (89.5% of the total weight) of toluene, 10,9 (37% of the total mass) of ethyl acetate and the first portion of the mixture of monomers constituting 30% of the total weight of the mixture of monomers.

The first portion of the mixture of monomers comprises, by wt.%: 7.4 butyl acrylate, 6.6 methacrylate, 1.65 styrene, 0,84 methacrylic acid. The ratio of monomers is 45:40:10:5.

Previously in the first portion of the monomers is dissolved first portion of azodyes is butyronitrile in the amount of 0.03 wt.%, that is 3% of the total weight of azodiisobutyronitrile. Then the temperature in the reactor was raised to 78-80°and maintain the reaction mass at this temperature for 1.5 hours.

After that, the reactor serves the second portion of azodiisobutyronitrile, comprising 17% of the total weight of the initiator. The second portion of the initiator is a pre-prepared solution in a solvent mixture containing, wt.%: 0,19 azodiisobutyronitrile, 0,3 (2% of the total weight) of toluene, 2,9 (10% of the total mass) of ethyl acetate. After the introduction of the second portion of initiator, the reaction mass can withstand 30 minutes at a temperature of synthesis.

In the second stage copolymerization into the reactor at a temperature synthesis 78-80°C for 5 hours parallel to dispense a second portion of the mixture of monomers and a third portion of azodiisobutyronitrile. The second portion of the mixture of monomers is 70% of the total weight of the monomers and includes, in wt.%: 17.3 butyl acrylate, 15.4 methacrylate, 3.85 styrene, 1,9 methacrylic acid. The ratio of monomers is 45:40:10:5.

The third portion of azodiisobutyronitrile is 80% of the total mass of the initiator and is a pre-prepared solution comprising, by wt.%: 0.88 azodiisobutyronitrile, 0,3 (8.5% of the total weight) of toluene and 15.6 (53% of the total mass) of ethyl acetate. At the end of the dosing conduct exposure for 1.5 is aces. The ratio of toluene and ethyl acetate at the end of the 2nd stage copolymerization is 0.1:1. The ratio of the mixture of monomers to the solvent mixture is 1.7:1.

Upon reaching a conversion of 84% in the reaction mass injected 10%solution of a copolymer of butyl acrylate, styrene and methacrylic acid, taken in the ratio of 42:57:1 mixture of toluene and ethanol, taken in the ratio 1:1. The amount of copolymer is 1.8% of the nominal concentration of the copolymer at the end of the 2nd stage copolymerization.

After the introduction of the additional solution of the copolymer, the reaction mass is allowed to stand for 1 hour at a temperature of synthesis, after which the finished product is cooled and discharged.

Properties of the obtained film are shown in table 1.

Additionally shown in tables 2-4 contain signs of a method of obtaining a film-forming agent.

Table 1
Properties of the obtained film-forming agent
# exampleMass fraction of non-volatiles, wt.%

GOST 17537
Viscosity srvc., with VZ-246 nozzle (4) GOST 8420Adhesion, b

GOST 15140
The film hardness by pendulum device DOE -3 GOST 5233 $ The duration of drying up to 3 in (20±2)#x000B0; With

GOST 19007
Water resistance, hour GOST 9403-80

Method Δ
Water absorption, wt.% 1 hour

OST 10086-M, AND 32
Abrasion resistance, kg/mm

GOST 20811-75
144,623,010,4420More than 4000,2More than 20
242,91610,43254000,2More than 20
361,522010,41304000,2More than 20
45050,310,40354000,2More than 20
544,623,010,40304000,3More than 20
658,714110,30354000,3More than 20
756,513710,32304000,2More than 20
The placeholder 40,0103

420
10,2590Not spand.1,82

Table 2

I stage copolymerization
# exampleThe estimated concentration of the final product, wt.%Dose I ΣM. wt.%The initiator, wt.%Toluene, wt.%The ethyl acetate, wt.%The concentration of the copolymer, wt.%
OnlyI dose2 servingLoading into the reactor,theOn the dissolution of 2 servings initiatorLoading into the reactor,theOn the dissolution of 2 servings initiator
144,6154,5520892,591322,4
242,910521597390108,2
361,520322090,5135 1337,4
4a 50.5302317to 89.52371036,7
544,6154,5520892,5321318,7
658,6154,5520892,5321330,6
756,5302317to 89.52371049
Note: Σ M is the sum of the monomers;

The conversion of monomers, %
Table 3
II stage copolymerization
# exampleΣ M 2nd portion, wt.%The initiator of the 3rd portion, wt.%Toluene to dissolve the 3rd portion of the initiator, wt.%The ethyl acetate dissolution of the 3rd portion of the initiator, wt.%The concentration of the copolymer, wt.%Ratio
Toluene: ethyl acetateΣM:ΣP
185758,555541:11:182
29083--48,20,9:11:183
380788,55266,80,9:12:184
470808,55356,50,9:11,3:185
585758,55550,71:11:183
685758,55566,6of 0.5:1a 1.8:182
770808,55362,40,1:1the 1.7:184
Note: ΣM is the sum of the monomers;
ΣP is the amount of solvents

Table 4
The introduction of additional copolymer
# exampleThe number of input copolymer, % of the concentration of the basic copolymerThe concentration of the solution was injected copolymer, wt.%The ratio of solvent
128Toluene: ethyl acetate: butanol: ethanol= 1:3:2:2
2413,0Toluene: butanol: ethanol = 1:0,5:0,5
32,6316,5Toluene: acetone = 1:1
41,88Toluene: butanol = 1:1
52,28Toluene: ethanol = 1:1
6of 2.26the 13.4Toluene: butanol: ethanol = 1:0,5:0,5
71,7710Toluene: ethanol = 1:1

1. The method of obtaining the acrylic film-forming agent, comprising the copolymerization of (meth)acrylic monomers and styrene in the presence of a radical initiator type in the environment of an organic solvent, characterized in that the implement two-stage copolymerization of butyl acrylate, methyl methacrylate, styrene and methacrylic acid in a ratio (40-45):(40-4):(10-14):(1-5) in a mixture of toluene and ethyl acetate at a ratio of 0.1 to 1.0):1 with portions of the filing of a mixture of monomers in stages: the first stage - 10-30%, the second - 70-90% of the total mass of the monomers and the initiator during multiple exposure of the reaction mixture, and after reaching a conversion of the monomers 82-85% additionally introduce a solution of a copolymer of butyl acrylate, styrene and methacrylic acid in the ratio of monomers in the copolymer 42:57:1 mixture of toluene and butanol or ethanol, or toluene and acetone, or toluene, ethyl acetate, ethanol and butanol, and the copolymer of butyl acrylate, styrene and methacrylic acid is administered in the amount of 1,77-4.0 wt.%, calculated from the concentration of the basic copolymer.

2. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that the two-stage copolymerization of butyl acrylate, methyl methacrylate, styrene and methacrylic acid is carried out at a ratio of monomers and solvents (1-2):1.

3. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that as the initiator of the use of azodiisobutyronitrile in the amount of 2-5% by weight of the total monomers.

4. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that prior to the copolymerization was charged to the reactor 89-97% by weight of toluene and 9-90% by weight of ethyl acetate.

5. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that the first portion of the initiator is dissolved in a mixture of butyl acrylate, methyl methacrylate,styrene and methacrylic acid, the reaction mass is heated to 78-80°C and maintained for 1.5 hours

6. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that the second portion of initiator in the amount of 15-20% of the total mass of initiator fed into the reactor in the form of a solution in a solvent mixture containing from 1.0 to 3.0% by weight of toluene and 10-13% by weight of ethyl acetate, and incubated the reaction mass for 30 minutes at a temperature of synthesis.

7. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that the second portion of the mixture of monomers is metered in over 5 hours with pre-dissolved in a third portion of the initiator or the second portion of the mixture of monomers is metered in over 5 h in parallel with the solution of the third portion of the initiator in a mixture of toluene and ethyl acetate, taken in a ratio of 8.5:(52-55), and the third portion of the initiator is 75-83% of its mass, and after the dosing of the components of the reaction mass incubated 1.5 h at a temperature of synthesis.

8. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that, after introduction of the solution of a copolymer of butyl acrylate, styrene and methacrylic acid, the reaction mass is allowed to stand for 1 h at a temperature of synthesis.

9. The method of obtaining the acrylic film-forming agent according to claim 1, characterized in that the copolymer of butyl acrylate, styrene and methacrylic acid is injected into the de solution with a concentration of 8-16,5 wt.% in a mixture of toluene and butanol at a ratio of 1:1, or toluene and ethanol at a ratio of 1:1, or toluene, ethanol and butanol at a ratio of 1:0,5:0,5, or toluene and acetone at a ratio of 1:1, or toluene, ethyl acetate, ethanol and butanol at a ratio of 1:3:2:2.



 

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