CN114874392A - Preparation method of ACS resin - Google Patents

Abstract

The invention belongs to the technical field of resin preparation. The invention provides a preparation method of ACS resin, which comprises the steps of mixing chlorinated polyethylene, an unsaturated nitrile monomer, a monoalkyl vinyl aromatic monomer, a comonomer and a solvent to obtain a rubber solution; mixing a rubber solution, an initiator, an antioxidant, a lubricant and a heat stabilizer in an oxygen-containing atmosphere, and then carrying out one-step polymerization reaction to obtain a polymer melt; or mixing the rubber solution, the initiator, the antioxidant, the lubricant and the heat stabilizer in an oxygen-containing atmosphere, and then carrying out continuous bulk polymerization reaction to obtain a polymer melt; and devolatilizing the polymer melt to obtain the ACS resin. The present invention introduces oxygen-containing gas into the polymerization system for synthesizing ACS resin, and the oxygen-containing gas and the initiator act together to initiate bulk or solution polymerization. The method provided by the invention has the advantages that the time for the polymerization process is short, the intermittent operation and the continuous operation can be realized, and the prepared ACS resin has higher impact resistance and surface gloss.

Description

Preparation method of ACS resin

Technical Field

The invention relates to the technical field of resin preparation, in particular to a preparation method of ACS resin.

Background

Although ABS resins have excellent properties such as moldability, impact resistance and gloss, butadiene rubbers used in the synthesis of ABS resins contain a double bond structure and are therefore easily decomposed and oxidized by ultraviolet rays, heat energy and the like, and when used for a long period of time in places where weather resistance is required, physical properties may be deteriorated and discoloration may occur. Although additives may be used to solve this problem, the stabilizer has a limited effect on the long-term stability of the resin, and the most fundamental solution is to use a rubber containing no unsaturated double bonds instead of the butadiene rubber in the ABS resin. Based on the above idea, researchers have developed ACS resins by replacing polybutadiene rubber in ABS resins with saturated chlorinated polyethylene rubber (CPE) bodies. The ACS resin belongs to special ABS resin, inherits the excellent mechanical property, processability and electrical property of the ABS resin, and has excellent weather resistance, flame retardant property and antistatic property.

The preparation method of the ACS resin is basically the same as that of the ABS resin, and the ACS resin can be produced by a blending method or a direct method. The blending method is to mix the chlorinated polyethylene rubber and the styrene-acrylonitrile copolymer (SAN resin) in a molten state by using a compatibilization technology, and has the advantages of simple process and poor product performance. Therefore, the direct process is mainly used industrially for the production of ACS resins. The ACS resin produced by the direct method has two technical routes of a suspension-blending method and a continuous bulk method. The suspension-blending process is similar to the emulsion-blending process commonly used in the industry for producing ABS resins. Firstly, chlorinated polyethylene rubber graft styrene-acrylonitrile copolymer powder (CPE-g-SAN polymer rubber powder) is synthesized by a suspension polymerization method, and then the graft copolymer is blended with styrene-acrylonitrile copolymer (SAN resin) synthesized by continuous bulk polymerization to obtain the ACS resin. The other technical route is a continuous bulk method, which is basically the same as the technique for producing ABS resin by the continuous bulk method, firstly, chlorinated polyethylene rubber, monomer styrene, acrylonitrile and solvent are mixed into solution, initiator and other additives are added, then the solution is conveyed into a continuous polymerization reactor to carry out free radical copolymerization reaction to synthesize SAN resin and CPE-g-SAN graft copolymer, and the product ACS resin is obtained through devolatilization and granulation. In the early days, the suspension-blending method was mainly used in the industry to produce ACS resin, and in recent years, the process has been replaced by a more environment-friendly continuous bulk polymerization process because of the large amount of waste water generated and serious environmental pollution, which is difficult to meet the increasingly severe environmental requirements of the world. The continuous bulk polymerization technology has the advantages of short process route, continuous polymerization process, stable product quality, low VOC content, less three wastes and environmental protection, but the ACS resin produced by the method has mechanical property and surface gloss inferior to those of the suspension-blending method. This disadvantage severely limits the range of applications for continuous bulk ACS resins.

A great deal of research shows that the poor mechanical property and the poor surface gloss of the ACS resin produced by the bulk polymerization method are caused by the fact that the grafting rate of the CPE-g-SAN graft copolymer synthesized in the bulk polymerization process is lower than that of the product produced by the suspension method. The low grafting ratio results in poor compatibility of the rubber phase with the SAN resin of the matrix and a larger phase zone size of the rubber phase, resulting in poor mechanical properties and surface gloss of the ACS resin. The reasons for the low grafting rate of the CPE-g-SAN graft copolymer formed when the ACS resin is synthesized by the bulk method are as follows: firstly, when the ACS resin is synthesized by continuous bulk polymerization, the grafting reaction mainly occurs before phase inversion, and the grafting reaction is basically stopped after the phase inversion occurs; secondly, chlorinated polyethylene CPE is in a saturated structure, which is not beneficial to the grafting reaction, and only active atoms on CPE chains can be captured by free radicals to form grafting points to initiate monomer polymerization or generate coupling reaction with other chain free radicals to form branched chains. Based on the above-mentioned shortcomings of the bulk polymerization method, researchers have conducted a lot of experiments to improve the grafting rate of the CPE-g-SAN graft copolymer when the ACS resin is synthesized by the bulk polymerization method. At present, the most effective method is to reduce the initiator concentration of the system and increase the grafting reaction time. The method is simple, namely, the initiator is added in batches instead of once, and the grafting rate is improved by reducing the concentration of free radicals in the system, prolonging the reaction time and reducing the chain termination reaction. The method can improve the grafting rate of the CPE-g-SAN graft copolymer and improve the mechanical property when the ACS resin is synthesized by a bulk method to a certain extent, but the reaction time is longer, needs more than 20 hours, and is not suitable for industrial production; in addition, the molecular weight of the SAN resin obtained by polymerization is increased seriously by adopting the method while the grafting ratio of the CPE-g-SAN graft copolymer is improved, and the processing flowability of the product is reduced.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a preparation method of ACS resin.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of ACS resin, which comprises the following steps:

(1) mixing chlorinated polyethylene, an unsaturated nitrile monomer, a monoalkyl vinyl aromatic hydrocarbon monomer, a comonomer and a solvent to obtain a rubber solution;

(2) mixing a rubber solution, an initiator, an antioxidant, a lubricant and a heat stabilizer in an oxygen-containing atmosphere, and then carrying out one-step polymerization reaction to obtain a polymer melt; or mixing the rubber solution, the initiator, the antioxidant, the lubricant and the heat stabilizer in an oxygen-containing atmosphere, and then carrying out continuous bulk polymerization reaction to obtain a polymer melt;

(3) and devolatilizing the polymer melt to obtain the ACS resin.

Preferably, the Mooney viscosity of the chlorinated polyethylene in the step (1) is 45-100, and the content of chlorine element is 20-45 wt%;

in the step (1), the unsaturated nitrile monomer is one or more of acrylonitrile, methacrylonitrile and ethacrylonitrile;

in the step (1), the monoalkyl vinyl aromatic hydrocarbon monomer is one or more of styrene, alpha-methyl styrene, alpha-ethyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2, 4-dimethyl styrene, p-tert-butyl styrene, alpha-ethyl p-methyl styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene and 2, 4-dibromostyrene;

the comonomer in the step (1) is one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, lauryl methacrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, perfluoroalkyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, maleic anhydride, methacrylic anhydride, alkenyl succinic anhydride, acrylamide, methacrylamide, maleimide and N-phenyl maleimide;

in the step (1), the solvent is one or more of benzene, toluene, ethylbenzene and xylene.

Preferably, the mixing in the step (1) is carried out under the condition of stirring, the rotating speed of the stirring is 180-260 rpm, and the time is 2.5-3.5 h.

Preferably, the oxygen-containing atmosphere in the step (2) is oxygen, air, oxygen-nitrogen binary gas or oxygen-argon binary gas;

the pressure of the oxygen-containing atmosphere is 0.1-1 MPa;

the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, diisopropylbenzene hydroperoxide, tert-butyl peroxybenzoate, cyclohexanone peroxide, tert-butyl peroxyoctoate, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxytert-valerate and benzoyl peroxide;

the antioxidant is one or more of antioxidant 300, antioxidant BBM, antioxidant 1076, antioxidant CA, antioxidant 1010 and antioxidant 618;

the lubricant is one or more of ethylene bis stearamide, polyethylene wax and methyl silicone oil;

the heat stabilizer is one or more of monobutyl maleate dibutyltin, dibutyltin dilaurate, di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, maleic acid di-n-octyl tin polymer and organic antimony heat stabilizer JT-1015.

Preferably, the mass parts of the raw materials are as follows: 15-35 parts of chlorinated polyethylene, 14-29 parts of unsaturated nitrile monomer, 46-66 parts of monoalkyl vinyl aromatic hydrocarbon monomer, 0-10 parts of comonomer, 20-40 parts of solvent, 0.01-0.1 part of initiator, 0.05-0.5 part of antioxidant, 0.1-0.5 part of lubricant and 0.5-2 parts of heat stabilizer.

Preferably, the temperature of the one-step polymerization reaction in the step (2) is 90-200 ℃, and the time is 2-20 h.

Preferably, the continuous bulk polymerization in the step (2) is to mix the rubber solution and the initiator, sequentially perform a first polymerization reaction, a second polymerization reaction and a third polymerization reaction to obtain a mixture, and then mix the mixture, the antioxidant, the lubricant and the heat stabilizer to perform a fourth polymerization reaction;

the feeding amount of the first polymerization reaction is 10-25 Kg/h;

the temperature of the first polymerization reaction and the temperature of the second polymerization reaction are independent from 90 ℃ to 180 ℃, and the time is independent from 1 hour to 2 hours;

the first polymerization reaction and the second polymerization reaction are carried out under the stirring condition, and the stirring rotating speed is independently 20-500 rpm.

Preferably, the temperature of the third polymerization reaction is 90-200 ℃, and the time is 1-2 h;

the third polymerization reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 60-200 rpm.

Preferably, the temperature of the fourth polymerization reaction is 180-200 ℃, and the time is 1-2 h;

the fourth polymerization reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 0-150 rpm.

Preferably, the temperature of devolatilization in the step (3) is 180-220 ℃.

The invention provides a preparation method of ACS resin, which comprises the steps of mixing chlorinated polyethylene, an unsaturated nitrile monomer, a monoalkyl vinyl aromatic monomer, a comonomer and a solvent to obtain a rubber solution; mixing a rubber solution, an initiator, an antioxidant, a lubricant and a heat stabilizer in an oxygen-containing atmosphere, and then carrying out one-step polymerization reaction to obtain a polymer melt; or mixing the rubber solution, the initiator, the antioxidant, the lubricant and the heat stabilizer in an oxygen-containing atmosphere, and then carrying out continuous bulk polymerization reaction to obtain a polymer melt; and devolatilizing the polymer melt to obtain the ACS resin. The invention introduces oxygen-containing gas into a polymerization system for synthesizing the ACS resin, and the oxygen-containing gas and the initiator jointly act to initiate bulk or solution polymerization to prepare the ACS resin with high grafting rate and excellent mechanical property. The method provided by the invention has the advantages that the polymerization process is short, the intermittent operation and the continuous operation can be realized, the CPE-g-SAN copolymer obtained by polymerization has higher grafting ratio, and the prepared ACS resin has higher impact resistance and surface gloss and excellent comprehensive performance.

Drawings

FIG. 1 is a flow chart of the continuous bulk polymerization process for preparing ACS resin according to the present invention.

Detailed Description

The invention provides a preparation method of ACS resin, which comprises the following steps:

(1) mixing chlorinated polyethylene, an unsaturated nitrile monomer, a monoalkyl vinyl aromatic hydrocarbon monomer, a comonomer and a solvent to obtain a rubber solution;

(2) mixing a rubber solution, an initiator, an antioxidant, a lubricant and a heat stabilizer in an oxygen-containing atmosphere, and then carrying out one-step polymerization reaction to obtain a polymer melt; or mixing the rubber solution, the initiator, the antioxidant, the lubricant and the heat stabilizer in an oxygen-containing atmosphere, and then carrying out continuous bulk polymerization reaction to obtain a polymer melt;

(3) and devolatilizing the polymer melt to obtain the ACS resin.

In the invention, the Mooney viscosity of the chlorinated polyethylene in the step (1) is preferably 45-100, more preferably 60-90, and more preferably 70-80; the content of chlorine element is preferably 20 to 45 wt%, more preferably 25 to 40 wt%, and still more preferably 30 to 35 wt%.

In the present invention, the unsaturated nitrile monomer in step (1) is preferably one or more of acrylonitrile, methacrylonitrile and ethacrylonitrile, and when the unsaturated nitrile monomer contains several components at the same time, the mass of each component is preferably equal.

In the present invention, the monoalkyl vinyl aromatic hydrocarbon monomer in step (1) is preferably one or more of styrene, α -methylstyrene, α -ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, p-tert-butylstyrene, α -ethyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene and 2, 4-dibromostyrene, and when the monoalkyl vinyl aromatic hydrocarbon monomer contains several components at the same time, the mass of each component is preferably equal.

In the present invention, the comonomer in step (1) is preferably acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, perfluoroalkyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, maleic anhydride, methacrylic anhydride, alkenyl succinic anhydride, acrylamide, methacrylamide, maleimide and N-phenyl maleimide, wherein the comonomers comprise one or more of the components simultaneously, and the mass of each component is preferably equal.

In the present invention, the solvent in step (1) is preferably one or more of benzene, toluene, ethylbenzene and xylene.

In the invention, the mixing in the step (1) is preferably carried out under stirring conditions, and the stirring rotation speed is preferably 180-260 rpm, more preferably 190-250 rpm, and more preferably 200-240 rpm; the time is preferably 2.5 to 3.5 hours, more preferably 2 to 3 hours, and still more preferably 2.4 to 2.6 hours.

In the present invention, the oxygen-containing atmosphere in the step (2) is preferably oxygen, air, an oxygen-nitrogen binary gas, or an oxygen-argon binary gas.

In the present invention, the pressure of the oxygen-containing atmosphere is preferably 0.1 to 1MPa, more preferably 0.2 to 0.8MPa, and still more preferably 0.4 to 0.6 MPa.

In the present invention, the initiator is preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, diisopropylbenzene hydroperoxide, tert-butyl peroxybenzoate, cyclohexanone peroxide, tert-butyl peroxyoctoate, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxytert-valerate and benzoyl peroxide, and when the initiator comprises several components at the same time, the mass of each component is preferably equal.

In the present invention, the antioxidant is preferably one or more of antioxidant 300, antioxidant BBM, antioxidant 1076, antioxidant CA, antioxidant 1010 and antioxidant 618, and when the antioxidant comprises several components at the same time, the mass of each component is preferably equal.

In the present invention, the lubricant is preferably one or more of ethylene bis stearamide, polyethylene wax and methyl silicone oil, and when the lubricant contains several components at the same time, the mass of each component is preferably equal to that of the other component

In the present invention, the heat stabilizer is preferably one or more of monobutyl maleate dibutyltin, dibutyltin dilaurate, di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, di-n-octyl tin maleate polymer and organic antimony heat stabilizer JT-1015, and when the heat stabilizer comprises several components at the same time, the quality of each component is preferably equal.

In the present invention, the raw materials are preferably as follows in parts by mass: 15-35 parts of chlorinated polyethylene, 14-29 parts of unsaturated nitrile monomer, 46-66 parts of monoalkyl vinyl aromatic hydrocarbon monomer, 0-10 parts of comonomer, 20-40 parts of solvent, 0.01-0.1 part of initiator, 0.05-0.5 part of antioxidant, 0.1-0.5 part of lubricant and 0.5-2 parts of heat stabilizer.

In the present invention, the chlorinated polyethylene is preferably 15 to 35 parts, more preferably 20 to 30 parts, and still more preferably 24 to 26 parts.

In the present invention, the unsaturated nitrile monomer is preferably 14 to 19 parts, more preferably 15 to 18 parts, and still more preferably 16 to 17 parts.

In the present invention, the monoalkyl vinyl aromatic monomer is preferably 46 to 66 parts, more preferably 50 to 62 parts, and more preferably 55 to 57 parts.

In the present invention, the comonomer is preferably 0 to 10 parts, more preferably 2 to 8 parts, and still more preferably 4 to 6 parts.

In the present invention, the solvent is preferably 20 to 40 parts, more preferably 25 to 35 parts, and still more preferably 28 to 32 parts.

In the present invention, the initiator is preferably 0.01 to 0.1 part, more preferably 0.02 to 0.08 part, and still more preferably 0.04 to 0.06 part.

In the present invention, the antioxidant is preferably 0.05 to 0.5 part, more preferably 0.1 to 0.4 part, and even more preferably 0.2 to 0.3 part.

In the present invention, the lubricant is preferably 0.1 to 0.5 part, more preferably 0.2 to 0.4 part, and still more preferably 0.25 to 0.35 part.

In the present invention, the heat stabilizer is preferably 0.5 to 2 parts, more preferably 1 to 1.5 parts, and still more preferably 1.2 to 1.3 parts.

In the invention, before the one-step polymerization reaction, the rubber solution is pre-stirred, wherein the pre-stirring rotating speed is preferably 20-500 rpm, preferably 100-400 rpm, and more preferably 200-300 rpm; the pre-stirring time is preferably 10-20 min, more preferably 12-18 min, and more preferably 14-16 min, after the pre-stirring is finished, introducing oxygen-containing gas, and changing the reaction environment into an oxygen-containing atmosphere, wherein the stirring speed is preferably 100-180 rpm, more preferably 110-170 rpm, and more preferably 130-150 rpm; and simultaneously raising the temperature to the temperature of the one-step polymerization reaction for reaction, wherein the time for raising the temperature is preferably 0.5-1.5 h, more preferably 0.6-1.4 h, and more preferably 0.8-1.2 h.

In the invention, the temperature of the one-step polymerization reaction in the step (2) is preferably 90-200 ℃, more preferably 120-160 ℃, and more preferably 130-150 ℃; the time is preferably 2-20 h, more preferably 3-10 h, and even more preferably 4-8 h; and (4) preserving the heat after the one-step polymerization reaction is finished.

In the invention, the temperature of the heat preservation is preferably 180-200 ℃, more preferably 185-195 ℃, and more preferably 188-192 ℃; the heat preservation time is preferably 1-2 hours, more preferably 1.2-1.8 hours, and even more preferably 1.4-1.6 hours. And obtaining a polymer melt after the heat preservation is finished.

In the present invention, the continuous bulk polymerization in the step (2) is preferably performed by mixing the rubber solution and the initiator, and then performing a first polymerization, a second polymerization, and a third polymerization in this order to obtain a mixture, and then performing a fourth polymerization after mixing the mixture, the antioxidant, the lubricant, and the heat stabilizer.

In the invention, the first polymerization reaction is carried out in a first helical ribbon type reaction kettle, and oxygen-containing gas is introduced into the first reaction kettle.

In the invention, after being uniformly mixed, the rubber solution and the initiator are conveyed into a first reaction kettle by a conveying device, wherein the feeding amount of the first polymerization reaction is preferably 10-25 Kg/h, more preferably 15-20 Kg/h, and more preferably 16-19 Kg/h.

In the invention, after the first polymerization reaction is finished, the mixture is conveyed into a second reaction kettle by a conveying device to carry out a second polymerization reaction.

In the invention, the temperature of the first polymerization reaction and the second polymerization reaction is preferably 90-180 ℃, more preferably 110-160 ℃, and even more preferably 130-140 ℃ independently; the time is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and even more preferably 1.4 to 1.6 hours.

In the present invention, the first polymerization reaction and the second polymerization reaction are preferably carried out under stirring conditions, and the rotation speed of the stirring is independently preferably 20 to 500rpm, more preferably 100 to 400rpm, and still more preferably 200 to 300 rpm.

In the invention, after the second polymerization reaction is finished, the mixture is conveyed into a third reaction kettle by a conveying device for a third polymerization reaction.

In the invention, the temperature of the third polymerization reaction is preferably 90-200 ℃, more preferably 120-180 ℃, and more preferably 140-160 ℃; the time is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.

In the present invention, the third polymerization reaction is preferably performed under a stirring condition, and the rotation speed of the stirring is preferably 60 to 200rpm, more preferably 100 to 160rpm, and even more preferably 120 to 140 rpm.

In the invention, after the third polymerization reaction is finished, the mixture is conveyed into a fourth reaction kettle by a conveying device, an antioxidant, a lubricant and a heat stabilizer are added at an inlet of the fourth reaction kettle, the antioxidant, the lubricant and the heat stabilizer are uniformly mixed and then added, the feeding amount is preferably 0.8-2.4 Kg/h, more preferably 1-2 Kg/h, and even more preferably 1.4-1.6 Kg/h.

In the invention, the temperature of the fourth polymerization reaction is preferably 180-200 ℃, more preferably 185-195 ℃, and more preferably 186-194 ℃; the time is preferably 1 to 2 hours, more preferably 1.2 to 1.8 hours, and still more preferably 1.4 to 1.6 hours.

In the present invention, the fourth polymerization reaction is preferably performed under a stirring condition, and the rotation speed of the stirring is preferably 0 to 150rpm, more preferably 50 to 100rpm, and even more preferably 60 to 90 rpm.

In the invention, the polymer melt enters a devolatilization extruder to be extruded and granulated, so as to obtain the ACS resin.

In the invention, the temperature of the devolatilization in the step (3) is preferably 180-220 ℃, more preferably 190-210 ℃, and even more preferably 195-205 ℃.

The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

Adding 19 parts of acrylonitrile, 56 parts of styrene, 25 parts of chlorinated polyethylene and 30 parts of toluene into a reaction kettle, starting stirring at the rotating speed of 240rpm, stirring for 3 hours at normal temperature, adding 0.1 part of di-tert-butyl peroxide, 0.05 part of antioxidant 1076, 0.32 part of methyl silicone oil and 0.85 part of dibutyltin dilaurate, keeping the rotating speed, continuously stirring for 15 minutes, introducing nitrogen to remove air in the kettle, introducing 0.2MPa of nitrogen into the kettle, continuously heating at the stirring speed of 140rpm for 1 hour to 130 ℃, and carrying out one-step polymerization reaction for 4 hours; after the reaction was completed and maintained at 180 ℃ for 1 hour, the obtained melt was devolatilized at 200 ℃, extruded and pelletized to obtain ACS resin pellets, the graft ratio was measured by gravimetric method and the gloss and impact properties of the ACS resin were tested using the corresponding ASTM standard, and the results are reported in table 1.

Example 2

Adding 15 parts of methacrylonitrile, 60 parts of alpha-methylstyrene, 25 parts of chlorinated polyethylene, 5 parts of methacrylic acid and 35 parts of ethylbenzene into a reaction kettle, starting stirring at a rotating speed of 180rpm, stirring at normal temperature for 2.5 hours, then adding 0.08 part of azobisisobutyronitrile, 0.2 part of antioxidant 1010, 0.42 part of ethylene bis-stearamide and 1.43 parts of maleic acid monobutyl dibutyl tin, keeping the rotating speed for stirring continuously for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.5MPa of nitrogen into the kettle, keeping the stirring speed at 160rpm, continuously heating for 1.3 hours to 150 ℃, and carrying out one-step polymerization reaction for 12 hours; after the reaction was completed, the reaction was maintained at 190 ℃ for 1.5 hours, and the obtained melt was devolatilized at 190 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 3

Adding 16 parts of ethyl acrylonitrile, 66 parts of alpha-ethyl styrene, 18 parts of chlorinated polyethylene and 26 parts of toluene into a reaction kettle, starting stirring at the rotating speed of 230rpm, stirring for 3 hours at normal temperature, then adding 0.06 part of azodiisoheptonitrile, 0.23 part of antioxidant 618, 0.41 part of ethylene bis stearamide and 1.2 parts of maleic acid monobutyl ester dibutyltin, keeping the rotating speed for continuously stirring for 10 minutes, introducing nitrogen to remove air in the kettle, introducing 0.8MPa of nitrogen into the kettle at the stirring speed of 160rpm, continuously heating for 1.2 to 160 ℃, and carrying out one-step polymerization for 15 hours; after the reaction was completed and maintained at 195 ℃ for 1.5 hours, the resultant melt was devolatilized at 190 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 4

Adding 16 parts of methacrylonitrile, 50 parts of o-methylstyrene, 34 parts of chlorinated polyethylene and 20 parts of ethylbenzene into a reaction kettle, starting stirring at the rotation speed of 190rpm, stirring for 3.2 hours at normal temperature, then adding 0.06 part of tert-butyl peroxybenzoate, 0.1 part of antioxidant 1076, 0.2 part of ethylene bis stearamide and 0.88 part of di-n-octyl tin maleate, keeping the rotation speed for continuously stirring for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.3MPa of nitrogen into the kettle at the stirring speed of 100rpm, continuously heating for 1.5 hours to 120 ℃, and carrying out one-step polymerization for 5 hours; after the reaction was completed and maintained at 200 ℃ for 1.5 hours, the obtained melt was devolatilized at 205 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 5

Adding 19 parts of methacrylonitrile, 60 parts of 2, 4-dimethyl styrene, 21 parts of chlorinated polyethylene, 2 parts of ethyl methacrylate and 23 parts of xylene into a reaction kettle, starting stirring at the rotation speed of 190rpm, stirring at normal temperature for 3.5 hours, then adding 0.06 part of tert-butyl peroxyneodecanoate, 0.4 part of antioxidant 618, 0.45 part of ethylene bis-stearamide and 2 parts of organic antimony heat stabilizer JT-1015, keeping the rotation speed for stirring continuously for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.6MPa of nitrogen into the kettle, stirring at the speed of 160rpm, continuously heating for 1.5 hours to 160 ℃, and carrying out one-step polymerization for 10 hours; after the reaction was completed and maintained at 195 ℃ for 2 hours, the resultant melt was devolatilized at 220 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 6

Adding 15 parts of acrylonitrile, 65 parts of p-tert-butylstyrene, 20 parts of chlorinated polyethylene, 10 parts of lauryl acrylate and 40 parts of toluene into a reaction kettle, starting stirring at the rotating speed of 260rpm, stirring at normal temperature for 2.5 hours, then adding 0.05 part of benzoyl peroxide, 0.4 part of antioxidant 1010, 0.2 part of ethylene bis-stearamide and 0.6 part of dibutyltin dilaurate, keeping the rotating speed for continuously stirring for 16 minutes, introducing nitrogen to remove air in the kettle, introducing 0.6MPa of nitrogen into the kettle at the stirring speed of 100rpm, continuously heating for 1.5 to 180 ℃, and carrying out one-step polymerization reaction for 8 hours; after the reaction was completed and maintained at 190 ℃ for 2 hours, the obtained melt was devolatilized at 200 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 7

Adding 15 parts of methacrylonitrile, 64 parts of alpha-ethyl p-methylstyrene, 21 parts of chlorinated polyethylene and 35 parts of xylene into a reaction kettle, starting stirring at the rotation speed of 190rpm, stirring for 3 hours at normal temperature, then adding 0.08 part of benzoyl peroxide, 0.3 part of antioxidant CA, 0.4 part of polyethylene wax and 1.4 parts of organic antimony heat stabilizer JT-1015, keeping the rotation speed, continuously stirring for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.5MPa of nitrogen into the kettle at the stirring speed of 180rpm, continuously heating for 1.5 hours to 170 ℃, and carrying out one-step polymerization reaction for 9 hours; after the reaction was completed and maintained at 200 ℃ for 2 hours, the obtained melt was devolatilized at 220 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 8

Adding 19 parts of ethyl acrylonitrile, 66 parts of o-chlorostyrene, 15 parts of chlorinated polyethylene and 27 parts of ethylbenzene into a reaction kettle, starting stirring at the rotation speed of 250rpm, stirring for 3 hours at normal temperature, then adding 0.04 part of diisopropylbenzene hydroperoxide, 0.32 part of antioxidant CA, 0.45 part of polyethylene wax and 2 parts of dibutyltin dilaurate, keeping the rotation speed, continuously stirring for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.9MPa of nitrogen into the kettle, continuously heating at the stirring speed of 180rpm for 1.5 to 200 ℃, and carrying out one-step polymerization reaction for 18 hours; after the reaction was completed, the reaction was maintained at 190 ℃ for 2 hours, and the obtained melt was devolatilized, extruded and pelletized at 200 ℃ to obtain ACS resin pellets, which were subjected to a performance test, and the results are recorded in table 1.

Example 9

Adding 19 parts of ethyl acrylonitrile, 46 parts of o-bromostyrene, 35 parts of chlorinated polyethylene, 7 parts of methyl methacrylate and 35 parts of toluene into a reaction kettle, starting stirring at the rotating speed of 260rpm, stirring at normal temperature for 3.5 hours, then adding 0.08 part of di-tert-butyl peroxide, 0.4 part of antioxidant 1076, 0.43 part of polyethylene wax and 1.6 parts of di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, keeping the rotating speed for continuously stirring for 10 minutes, introducing nitrogen to remove air in the kettle, introducing 0.8MPa of nitrogen into the kettle, continuously heating at the stirring speed of 170rpm for 0.5 to 160 ℃, and carrying out one-step polymerization reaction for 10 hours; after the reaction was completed and maintained at 180 ℃ for 1 hour, the obtained melt was devolatilized at 190 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 10

Adding 17 parts of acrylonitrile, 64 parts of 2, 4-dibromostyrene, 19 parts of chlorinated polyethylene, 3 parts of lauryl acrylate and 40 parts of toluene into a reaction kettle, starting stirring at a rotation speed of 195rpm, stirring at normal temperature for 2.5 hours, then adding 0.07 part of azobisisobutyronitrile, 0.23 part of antioxidant BBM, 0.4 part of polyethylene wax and 0.96 part of di-n-octyl-bis (mercaptoacetic acid, 2-ethylhexyl) tin, keeping the rotation speed, continuously stirring for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 0.7MPa of nitrogen into the kettle, continuously heating at the stirring speed of 180rpm for 0.5 to 90 ℃, and carrying out one-step polymerization reaction for 20 hours; after the reaction was completed and maintained at 190 ℃ for 1 hour, the obtained melt was devolatilized at 210 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 11

Adding 16 parts of methacrylonitrile, 54 parts of styrene, 30 parts of chlorinated polyethylene, 6 parts of acrylamide and 23 parts of toluene into a reaction kettle, starting stirring at the rotation speed of 190rpm, stirring for 2.8 hours at normal temperature, then adding 0.06 part of di-tert-butyl peroxide, 0.38 part of antioxidant 300, 0.42 part of polyethylene wax and 1.8 parts of di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, keeping the rotation speed, continuing stirring for 20 minutes, introducing nitrogen to remove air in the kettle, introducing 1MPa of nitrogen into the kettle at the stirring speed of 170rpm, continuously heating for 1.5 to 140 ℃, and carrying out one-step polymerization reaction for 12 hours; after the reaction was completed and maintained at 180 ℃ for 2 hours, the obtained melt was devolatilized at 220 ℃, extruded and pelletized to obtain ACS resin pellets, which were subjected to a performance test, and the results are reported in table 1.

Example 12

Stirring 19 parts of acrylonitrile, 56 parts of styrene, 25 parts of chlorinated polyethylene and 30 parts of toluene at the rotating speed of 240rpm for 3 hours, adding 0.1 part of di-tert-butyl peroxide, uniformly mixing, and sequentially conveying to a first, a second, a third and a fourth spiral-belt type reaction kettle by using conveying equipment for polymerization reaction, wherein the feeding amount is 19 Kg/h; introducing oxygen into the first reaction kettle, and maintaining the pressure at 0.1 MPa; the temperature in the first reaction kettle is 130 ℃, the rotating speed is 260rpm, and the reaction time is 1.5 h; the temperature in the second reaction kettle is 130 ℃, the rotating speed is 260rpm, and the reaction time is 1 h; the temperature in the third reaction kettle is 150 ℃, the rotating speed is 150rpm, and the reaction time is 1.5 h; adding 0.05 part of antioxidant 300, 0.32 part of ethylene bis stearamide and 0.85 part of dibutyl tin monobutyl maleate into an inlet of a fourth reaction kettle in proportion, wherein the feeding amount of an auxiliary agent is 1.8Kg/h, the temperature of the fourth reaction kettle is 180 ℃, the rotating speed is 120rpm, and reacting for 2 hours after all feeding is finished; and (3) allowing the material to enter a vacuum devolatilization system from an outlet of the fourth reaction kettle at the temperature of 200 ℃, recovering the solvent and unreacted monomers and reutilizing, and extruding and granulating the melt to obtain an ACS resin product. The graft ratio was measured gravimetrically and the gloss and impact properties of the ACS resin were tested using the corresponding ASTM standard and the results are reported in table 1.

Example 13

Stirring 15 parts of methacrylonitrile, 60 parts of m-methylstyrene, 25 parts of chlorinated polyethylene and 25 parts of toluene at the rotating speed of 190rpm for 3.5 hours, then adding 0.05 part of cyclohexanone peroxide, uniformly mixing, and sequentially conveying to a first, a second, a third and a fourth spiral-belt type reaction kettle by using conveying equipment for polymerization reaction, wherein the feeding amount is 19 Kg/h; introducing oxygen into the first reaction kettle, and maintaining the pressure at 0.4 MPa; the temperature in the first reaction kettle is 150 ℃, the rotating speed is 300rpm, the reaction time is 1.5h, the temperature in the second reaction kettle is 130 ℃, the rotating speed is 200rpm, and the reaction time is 2 h; the temperature in the third reaction kettle is 180 ℃, the rotating speed is 100rpm, and the reaction time is 1.5 h; adding 0.4 part of antioxidant BBM, 0.2 part of polyethylene wax and 1.25 parts of dibutyltin dilaurate into an inlet of a fourth reaction kettle in proportion, wherein the feeding amount of an auxiliary agent is 1.4Kg/h, the temperature of the fourth reaction kettle is 190 ℃, the rotating speed is 80rpm, and reacting for 2h after all feeding is finished; and (3) allowing the material to enter a vacuum devolatilization system from an outlet of the fourth reaction kettle at the temperature of 190 ℃, recovering the solvent and the unreacted monomer and reutilizing, and extruding and granulating the melt to obtain an ACS resin product. The graft ratio was measured gravimetrically and the gloss and impact properties of the ACS resin were tested using the corresponding ASTM standard and the results are reported in table 1.

Example 14

Stirring 14 parts of ethyl acrylonitrile, 66 parts of p-chlorostyrene, 20 parts of chlorinated polyethylene, 40 parts of xylene and 4 parts of methyl methacrylate at the rotating speed of 260rpm for 3.5 hours, then adding 0.08 part of azobisisobutyronitrile, uniformly mixing, and then sequentially conveying to a first, a second, a third and a fourth spiral-belt type reaction kettle by using conveying equipment for polymerization reaction, wherein the feeding amount is 20 Kg/h; introducing oxygen into the first reaction kettle, and maintaining the pressure at 0.8 MPa; the temperature in the first reaction kettle is 140 ℃, the rotating speed is 400rpm, the reaction time is 2 hours, the temperature in the second reaction kettle is 150 ℃, the rotating speed is 200rpm, and the reaction time is 1 hour; the temperature in the third reaction kettle is 190 ℃, the rotating speed is 140rpm, and the reaction time is 2 hours; adding 0.2 part of antioxidant 1076, 0.1 part of methyl silicone oil and 1.7 parts of organic antimony heat stabilizer JT-1015 into an inlet of a fourth reaction kettle in proportion, wherein the feeding amount of the auxiliary agent is 2.3Kg/h, the temperature of the fourth reaction kettle is 190 ℃, the rotating speed is 140rpm, and reacting for 2h after all feeding is finished; and (3) feeding the material into a vacuum devolatilization system from an outlet of the fourth reaction kettle at the temperature of 220 ℃, recovering the solvent and the unreacted monomer and reutilizing, and extruding and granulating the melt to obtain an ACS resin product. The graft ratio was measured gravimetrically and the gloss and impact properties of the ACS resin were tested using the corresponding ASTM standard and the results are reported in table 1.

TABLE 1 test results

As can be seen from the above examples, the present invention provides a process for the preparation of ACS resins by introducing an oxygen-containing gas into the polymerization system for the synthesis of ACS resins, which together with an initiator initiates the bulk or solution polymerization to achieve a grafting yield as high as 33.1% and an impact strength of 28.2KJ/m ² The ACS resin has higher impact resistance and surface gloss and excellent comprehensive performance.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for preparing an ACS resin, comprising the steps of:

(1) mixing chlorinated polyethylene, an unsaturated nitrile monomer, a monoalkyl vinyl aromatic hydrocarbon monomer, a comonomer and a solvent to obtain a rubber solution;

(2) mixing a rubber solution, an initiator, an antioxidant, a lubricant and a heat stabilizer in an oxygen-containing atmosphere, and then carrying out one-step polymerization reaction to obtain a polymer melt; or mixing the rubber solution, the initiator, the antioxidant, the lubricant and the heat stabilizer in an oxygen-containing atmosphere, and then carrying out continuous bulk polymerization reaction to obtain a polymer melt;

(3) and devolatilizing the polymer melt to obtain the ACS resin.

2. The method according to claim 1, wherein the chlorinated polyethylene in the step (1) has a Mooney viscosity of 45 to 100 and a chlorine content of 20 to 45 wt%;

in the step (1), the unsaturated nitrile monomer is one or more of acrylonitrile, methacrylonitrile and ethacrylonitrile;

in the step (1), the monoalkyl vinyl aromatic hydrocarbon monomer is one or more of styrene, alpha-methyl styrene, alpha-ethyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2, 4-dimethyl styrene, p-tert-butyl styrene, alpha-ethyl p-methyl styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene and 2, 4-dibromostyrene;

the comonomer in the step (1) is one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, isooctyl acrylate, lauryl methacrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, perfluoroalkyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, maleic anhydride, methacrylic anhydride, alkenyl succinic anhydride, acrylamide, methacrylamide, maleimide and N-phenyl maleimide;

in the step (1), the solvent is one or more of benzene, toluene, ethylbenzene and xylene.

3. The method according to claim 1 or 2, wherein the mixing in step (1) is performed under stirring conditions, wherein the stirring speed is 180 to 260rpm, and the stirring time is 2.5 to 3.5 hours.

4. The production method according to claim 3, wherein the oxygen-containing atmosphere in the step (2) is oxygen, air, an oxygen-nitrogen binary gas, or an oxygen-argon binary gas;

the pressure of the oxygen-containing atmosphere is 0.1-1 MPa;

the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, diisopropylbenzene hydroperoxide, tert-butyl peroxybenzoate, cyclohexanone peroxide, tert-butyl peroxyoctoate, lauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxytert-valerate and benzoyl peroxide;

the antioxidant is one or more of antioxidant 300, antioxidant BBM, antioxidant 1076, antioxidant CA, antioxidant 1010 and antioxidant 618;

the lubricant is one or more of ethylene bis stearamide, polyethylene wax and methyl silicone oil;

the heat stabilizer is one or more of monobutyl maleate dibutyl tin, dibutyl tin dilaurate, di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, di-n-octyl tin maleate polymer and organic antimony heat stabilizer JT-1015.

5. The preparation method according to claim 1, 2 or 4, characterized in that the raw materials are as follows in parts by mass: 15-35 parts of chlorinated polyethylene, 14-29 parts of unsaturated nitrile monomer, 46-66 parts of monoalkyl vinyl aromatic hydrocarbon monomer, 0-10 parts of comonomer, 20-40 parts of solvent, 0.01-0.1 part of initiator, 0.05-0.5 part of antioxidant, 0.1-0.5 part of lubricant and 0.5-2 parts of heat stabilizer.

6. The method according to claim 5, wherein the temperature of the one-step polymerization reaction in the step (2) is 90 to 200 ℃ and the time is 2 to 20 hours.

7. The method according to claim 5, wherein the continuous bulk polymerization in the step (2) is performed by mixing the rubber solution and the initiator, and then performing a first polymerization, a second polymerization, and a third polymerization in this order to obtain a mixture, and then performing a fourth polymerization after mixing the mixture, the antioxidant, the lubricant, and the heat stabilizer;

the feeding amount of the first polymerization reaction is 10-25 Kg/h;

the temperature of the first polymerization reaction and the temperature of the second polymerization reaction are independent from 90 ℃ to 180 ℃, and the time is independent from 1 hour to 2 hours;

the first polymerization reaction and the second polymerization reaction are carried out under the stirring condition, and the stirring rotating speed is independently 20-500 rpm.

8. The preparation method according to claim 7, wherein the temperature of the third polymerization reaction is 90-200 ℃ and the time is 1-2 h;

the third polymerization reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 60-200 rpm.

9. The method according to claim 7 or 8, wherein the fourth polymerization reaction is carried out at a temperature of 180 to 200 ℃ for 1 to 2 hours;

the fourth polymerization reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 0-150 rpm.

10. The method according to claim 9, wherein the devolatilization temperature in the step (3) is 180 to 220 ℃.

Images