CN113912782A - Preparation process of high impact polymer containing conjugated diene monomer - Google Patents

Preparation process of high impact polymer containing conjugated diene monomer Download PDF

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CN113912782A
CN113912782A CN202010649852.9A CN202010649852A CN113912782A CN 113912782 A CN113912782 A CN 113912782A CN 202010649852 A CN202010649852 A CN 202010649852A CN 113912782 A CN113912782 A CN 113912782A
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conjugated diene
polymerization
monomer
high impact
polymer
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李洋
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Chengdu 401 Technology Co ltd
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Chengdu 401 Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
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    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
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    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers

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Abstract

A preparation process of a high impact polymer containing conjugated diene monomers comprises the following steps of raw materials, by weight, 10 parts of a polymer obtained by polymerizing the conjugated diene monomers and 10-200 parts of a polymerized monomer containing carbon-carbon double bonds, wherein the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product. Utilize screw extrusion device mixing material, the heat dissipation problem in the control body polymerization process that not only can be convenient, the shearing efficiency of the different reaction stages of regulation that moreover can be very convenient possesses efficiently, and heat dissipation control is convenient to the convenient outstanding advantage of adjusting of shear strength.

Description

Preparation process of high impact polymer containing conjugated diene monomer
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a preparation process of a high impact polymer containing conjugated diene monomers.
Background
Impact resistance is a very important property of polymers. Polymers containing polybutadiene structures are among the most common impact-resistant materials for polymers, particularly ABS, due to their very low glass transition temperature and reasonable price. ABS is the most common engineering plastic used at present, and the annual output of the whole world exceeds eight million tons.
The conventional ABS production process includes an emulsion grafting step. The process requires a large amount of water consumption, and a large amount of auxiliary agents which help to form a stable emulsion remain in the product, affecting the properties of the final product, such as heat stability and color stability. The recent product line selects more continuous bulk method, and the bulk method has less polymerization impurities, less waste water and more environmental protection.
Since the polymerization of carbon-carbon double bonds is a strongly exothermic reaction, the viscosity increases after the start of the polymerization and heat dissipation is a very big challenge in bulk polymerization due to the lack of water as a dispersing system, and therefore the polymer raw material needs to be dissolved in the monomer at a lower temperature, usually at room temperature, and usually takes a long time to completely dissolve. And because different reaction stages require different temperatures, a multistage reaction device is usually adopted to control the conversion rate of each stage so as to reduce the concentrated release of heat, thus greatly influencing the reaction efficiency. For example, the Shanghai petrochemical institute reported in patent CN201110294499.8 a continuous bulk polymerization process for ABS resins, wherein the polymerization process exceeded 10 hours without including a dissolution step, and the entire process exceeded 20 hours with the dissolution step.
In addition, the particle size and the particle size distribution of the butadiene polymer serving as the rubber phase in the system have great influence on the performance of the final material, and the particle size distribution are closely related to stirring, so that the stirring design of each stage of reaction device is very critical, and the investment and the time cost for changing the stirring device for the reaction kettle device are very high.
As butadiene polymer is generally used as a raw material in bulk polymerization and reacts after being dissolved in a polymerization monomer, when the proportion of the raw material polymer is high, the solubility of the polymer in the monomer is limited, the compatibility is reduced, and in addition, the initial viscosity of a system is too large to be beneficial to dispersion, so that the ABS rubber phase prepared by the bulk method is not more than 20 percent generally, and the impact resistance of the product is difficult to further improve. In general, the bulk method is lower in cost and more advantageous, but still faces the problems of difficult heat dissipation, complex stirring control, difficult adjustment and limited rubber phase proportion.
Disclosure of Invention
The invention provides a preparation process of a high impact polymer containing conjugated diene monomers, aiming at the technical problems of heat management, shear control, low rubber phase content and the like in the bulk polymerization process control of high impact materials taking butadiene polymers such as ABS and the like as rubber phases. Utilize screw extrusion device mixing material, the heat dissipation problem in the control body polymerization process that not only can be convenient, the shearing efficiency of the different reaction stages of regulation that moreover can be very convenient, the high impact polymer plastics that use butadiene polymer as the rubber phase such as the preparation ABS of more convenient efficient possess efficient, and heat dissipation control is convenient to the convenient outstanding advantage of adjusting of shear strength.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of high impact polymer containing conjugated diene monomer comprises the following steps of (by weight parts) polymerizing 10 parts of polymer containing conjugated diene monomer and 3-200 parts of polymerized monomer containing carbon-carbon double bond;
the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product.
The method comprises the steps of uniformly mixing a polymer raw material obtained by polymerizing a conjugated diene monomer and a polymerization monomer containing a carbon-carbon double bond in a screw extrusion device, carrying out polymerization reaction of the carbon-carbon double bond on the polymerization monomer, carrying out graft reaction on the polymerization monomer and the carbon-carbon double bond in the polymer raw material to form a two-phase polymer, dispersing the two-phase polymer under the shearing action of a screw to form a prepolymer with good compatibility, and then continuously polymerizing in a subsequent polymerization device to obtain a polymer product.
At present, the most common screw extrusion device is a co-rotating twin-screw extruder, and the other screw extrusion devices with strong shearing and dispersing capacity can utilize the process of the invention to realize the production of high-impact materials.
The monomer of the polymer raw material contains not less than 20 mass percent of butadiene. The common raw material is at least one of butadiene rubber, styrene-butadiene rubber, nitrile rubber and SBS rubber. The raw materials contain not less than 20 mass percent of butadiene polymer, and the raw material dispersion system has certain viscosity and can adapt to the application of screw extrusion equipment, so that the mixing and dispersing process of the materials can be carried out in the screw extrusion equipment. The screw extrusion device has the shearing efficiency far exceeding that of the reaction kettle, and can effectively disperse and mix the reaction system even under the condition that the viscosity of the polymerization system is very high, so that the system is more uniform. The updating efficiency of the material interface in the screw device is hundreds of times of that of the reaction kettle, the timely emission of polymerization reaction heat can be ensured, and the high molecular weight part formed by polymerization can be quickly dispersed into the whole system, so that the advantages of the screw extrusion device can be fully exerted to solve the problems of heat release and low rubber phase ratio in the polymerization process.
The weight ratio of the polymer raw material to the polymerized monomer is less than 1: 1. the monomer proportion is high, and the heat release is many, uses screw extrusion device more to have the advantage.
The temperature of the two sections of barrel bodies close to the polymeric monomer feeding port of the screw extrusion device does not exceed 150 ℃. The reaction speed and the heat release can be better controlled.
The subsequent polymerization device is at least one of a screw extrusion device, a pipeline reaction device and a reaction kettle.
After the prepolymerization target is reached, the monomer conversion at this point is usually not more than 40%, and sufficient reaction time is required to further increase the monomer conversion. If the screw extrusion device is used for prolonging the reaction time, the purpose can be achieved only by a large length-diameter ratio, and the screw extrusion device can be applied to a pipeline reactor and a reaction kettle to prolong the reaction time in a product with low shearing requirement, so that the manufacturing difficulty of equipment is reduced, and the occupied area of the equipment is reduced.
Preferably, the subsequent polymerization apparatus comprises a pipeline reaction apparatus. The effective volume provided by the pipeline is fully utilized to prolong the reaction time, the product quality is more stable, and the complete continuous production can be realized.
Further preferably, the subsequent polymerization device is a plug flow pipeline reaction device and a screw extrusion device which are connected in sequence. And the screw enters a pipeline reaction device after finishing dispersion and prepolymerization, then enters a screw device, and further finishes particle size adjustment of rubber particles by shearing of the screw to finish final polymerization and granulation. The long diameter of the plug flow pipeline reaction device is larger, and the uniformity is better.
The invention firstly adds polymer raw materials from the front end of the screw extrusion device and then adds polymerization monomers.
The polymer raw material containing conjugated diene can flow under normal temperature through strong shearing of a screw, in addition, polybutadiene can have better fluidity by adding a small amount of solvent or increasing the temperature, and a barrel body is filled with butadiene polymer fluid before the volatile monomer raw material is added, so that the volatile raw material is prevented from volatilizing from a solid feed inlet of the barrel body.
When the mass proportion of the polymerizable monomer to the raw materials is more than 80%, it is preferable that the polymerizable monomer is fed in portions from different portions of the barrel of the screw extruder. When the proportion of the polymerized monomers exceeds 80%, the monomers are added in a concentrated manner, so that the polymerization heat release is large, the control difficulty is high, the requirement on the heat dissipation of equipment is high, and the concentrated heat release can be avoided by adopting a mode that the polymerized monomers are added in batches at different parts of a screw extruder barrel, so that the requirement of the process on the heat dissipation of the equipment is reduced.
In another preferred embodiment, the polymer raw materials are divided into batches and the polymerized monomers are prepolymerized in screw extrusion devices with different shearing strengths respectively and then converged into a subsequent polymerization device to complete the subsequent polymerization reaction together.
If the polybutadiene rubber phase has more than two different particle size distributions, the performance of the product can be greatly improved, the particle size distribution is mainly determined by shearing in a prepolymerization stage, two prepolymerizations are respectively carried out in two screw extrusion devices, the shearing strength of the two prepolymerizations is controlled to be different, two different particle size distributions exist, the two different particle size distributions are mixed together for further polymerization, and the mentioned final product has rubber phase particles with two different particle sizes. If the butadiene polymer starting material consists of two polybutadienes of different particle sizes, it is easier to obtain rubber phase particles of two different particle size distributions.
The overall length-diameter ratio of the screw extrusion device is not less than 60. Can be formed by multistage series connection, and ensures the dispersion effect of the system and enough reaction time.
The carbon-carbon double bond polymerization monomer comprises at least one of styrene, acrylonitrile, butadiene, isoprene, vinyl acetate, acrylate and methacrylate.
Preferably, the carbon-carbon double bond polymerized monomer is at least one of styrene and acrylonitrile.
After the prepolymerization is finished, other polymers are added into the screw extrusion device in a side feeding mode to prepare the polymer alloy.
The invention has the beneficial effects that:
1. the invention utilizes the advantage of high interface updating efficiency of the screw extrusion device, can improve the heat dissipation efficiency, enables the reaction to be easier to control and has higher efficiency, solves the heat release problem of diene high impact polymer plastics, can prepare products with rubber phase content far exceeding 20 percent, can enable the raw material polymer and the monomer to be uniformly mixed in a very short time due to the super-strong shearing dispersion capacity of the screw extrusion device, can save the time for dissolving the raw material polymer in the monomer, and greatly improves the production efficiency.
2. The shear dispersion effect in different reaction schedules can be conveniently and rapidly adjusted by changing the combination of threaded elements of the screw extrusion device, so that the aim of adjusting the dispersed particle size of a rubber phase in a polymer is fulfilled, a product with better impact resistance is prepared, and the problem of particle size distribution of diene high-impact polymer plastics is solved; in the prepolymerization stage of the process, the shear strength of the screw extrusion device is controlled, so that the raw material polymer and the monomer are prepolymerized in different screw devices respectively to form prepolymerization products in different states, and then are converged together to complete the subsequent polymerization process, thereby realizing the matching use of rubber phases with different types and particle sizes, and further improving the comprehensive performance of polymer products.
Detailed Description
In order to more clearly and specifically illustrate the technical solution of the present invention, the present invention is further described by the following embodiments. The following examples are intended to illustrate the practice of the present invention and are not intended to limit the scope of the invention.
Example 1
A preparation method of high impact polymer containing conjugated diene monomer comprises the following steps of (by weight parts) polymerizing 10 parts of polymer containing conjugated diene monomer and 3 parts of polymerized monomer containing carbon-carbon double bond;
the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product.
Example 2
A preparation method of high impact polymer containing conjugated diene monomer comprises the following steps of (by weight parts) polymerizing 10 parts of polymer containing conjugated diene monomer and 200 parts of polymerized monomer containing carbon-carbon double bond;
the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product.
The polymer raw material contains not less than 20% by mass of butadiene in the polymerized monomers.
The polymer raw material comprises at least one of polybutadiene rubber, styrene-butadiene rubber, nitrile rubber and SBS rubber.
The carbon-carbon double bond polymerization monomer comprises at least one of styrene, acrylonitrile, butadiene, isoprene, vinyl acetate, acrylate and methacrylate.
Monomers that can be used in the process, in addition to the above-mentioned styrene and acrylonitrile, butadiene, isoprene, vinyl acetate, acrylates, methacrylates, etc., monomers containing double bonds can be used to modify the properties of the high impact materials.
Example 3
A preparation method of high impact polymer containing conjugated diene monomer comprises the following steps of (by weight parts) polymerizing 10 parts of polymer containing conjugated diene monomer and 50 parts of polymerized monomer containing carbon-carbon double bond;
the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product.
Firstly, adding polymer raw materials from the front end of a screw extrusion device, and then adding a polymerization monomer.
The temperature of the two sections of barrel bodies close to the polymerized monomer feeding port of the screw extrusion device is not more than 150 ℃.
The weight ratio of the polymer raw material to the polymerized monomer is less than 1: 1.
after the prepolymerization is finished, adding other polymers into the screw extrusion device in a side feeding mode to prepare the polymer alloy.
Example 4
This example is based on example 1:
firstly, adding polymer raw materials from the front end of a screw extrusion device, and then adding a polymerization monomer.
The temperature of the two sections of barrel bodies close to the polymerized monomer feeding port of the screw extrusion device is not more than 150 ℃.
When the mass proportion of the polymerized monomer in the raw materials is more than 80%, the polymerized monomer is added in batches from different parts of a barrel of the screw extruder device, and the reaction heat release is controlled.
Example 5
This example is based on example 1:
firstly, adding polymer raw materials from the front end of a screw extrusion device, and then adding a polymerization monomer.
The polymer raw materials are pre-polymerized in batches and polymerized monomers are pre-polymerized in screw extrusion devices with different shearing strengths respectively, and then are gathered in a subsequent polymerization device to complete the subsequent polymerization reaction together.
The separate prepolymerization process can be carried out in a main screw extruder and a side feeding screw, or can be carried out by separately prepolymerizing partial main and sub-screws and then converging the partial main and sub-screws.
The particle size and the shearing of the rubber particles in the final product are closely related, and the shearing performance of different screw parts can be conveniently controlled by using different thread elements on the screw in a combined manner. Meanwhile, when strong shearing is not needed, the reaction time can be prolonged by a method of connecting a tubular reaction device or a kettle type reaction device in series, and a better conversion rate is achieved, so that the total length-diameter ratio of the screw device can be reduced, and the processing cost of the whole device is reduced.
Example 6
This example is based on example 1:
the overall length-diameter ratio of the screw extrusion device is not less than 60, and the screw extrusion device can be formed by connecting multiple stages in series.
The carbon-carbon double bond polymerization monomer is at least one of styrene and acrylonitrile. These two monomers are the most commonly used, the other monomers being usually added as a component for adjusting the properties.
When the mass ratio of the monomer to the polymer in the raw materials is about 9, the rubber phase content of the product is about 10% in consideration of the conversion rate of the monomer polymerization and other various factors, and when the rubber phase content is less than 6, the rubber phase content may exceed 20%, which is a ratio that cannot be achieved by the bulk polymerization of the reaction vessel. When the mass ratio of the monomers to the polymer in the starting materials is 0.15, the rubber phase content can reach 87% at the highest theoretical level, and at this ratio, the screw extruder can handle the reaction very well without the problem of excessive viscosity. Even at higher rubber phase contents, the process of the invention can be well handled, but too high a proportion of the rubber phase is too poor in heat resistance to be closer to the application of rubber, or serves as a rubber phase to toughen other plastics, and is not suitable and directly used as plastics.
When the ratio of the mass of the monomer to the mass of the polymer in the raw materials is more than 20, the rubber phase content is only about 5% at this time, and the impact resistance has been seriously deteriorated.
When the polymerization reaches a certain degree, the high impact polymer plastic melt is in the barrel of the screw extrusion device, and other polymers, fillers and auxiliaries can be added in a side material mode to prepare the polymer alloy at one time, so that the performance of the product can be adjusted in a larger range, and the subsequent modification process is saved.
The preparation process of the invention can add conventional catalyst synthesized by diene polymer or some additives such as antioxidant, lubricant, molecular weight regulator, etc. according to the requirement, or can directly complete polymerization reaction without adding additives. The preparation method is suitable for synthesizing various diene polymers, is not limited to the types listed in the examples, and has wide application range.
Example 7
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 60: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 60 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 150 ℃ and 250 ℃ after the 18 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin is 14 percent, and the notch impact strength is 190J/m.
Example 8
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 60: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 1 of 60 parts of mixed liquid of styrene and acrylonitrile, wherein the mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of polymerization monomers. After the materials are added, the temperature is controlled to be between 150 ℃ and 180 ℃ for prepolymerization reaction, the temperature is increased to be between 200 ℃ and 250 ℃ after the 18 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin is 14 percent, the compatibility of the material is poor, and the notch impact strength is 58J/m.
This example shows that the temperature is too high in the prepolymerization stage compared with that in example 7, which results in poor compatibility and obviously reduced toughness.
Example 9
Continuously adding 5 parts of polybutadiene rubber into a screw rod with the diameter of 65mm and 30 barrel sections from a head feed inlet through a weightless metering scale, wherein the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 30 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer.
The unit is provided with a side feeding system at the 11 th barrel. The side position material extruder is that a screw rod diameter is 65mm, totally 10 section barrels, and the draw ratio is 40: 1 co-rotating twin screw extruder. The screw element combination of the side feeding extruder is subjected to shear reinforcement, and the shear reinforcement is increased by 150mm compared with 45-degree kneading blocks in the front 10 barrel bodies in the main machine. Likewise, 5 parts of polybutadiene rubber are added into an extrusion device through a weightless metering scale, a melt is formed at the temperature of between room temperature and 100 ℃, and a pump is continuously added into a fourth section of cylinder body according to the weight ratio of 3: and 30 parts of a mixed liquid of styrene and acrylonitrile of 1. The mixed liquid contains an initiator accounting for 0.1 percent of the mass of the polymerized monomer, a molecular weight regulator accounting for 0.1 percent of the mass of the polymerized monomer and mineral oil accounting for 1 percent of the mass of the polymerized monomer, the materials of the 11 th section of the main screw extrusion equipment enter a main extrusion device after prepolymerization and are mixed with the materials conveyed from the front of the main extrusion equipment, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 250 ℃ after the 18 th section of the cylinder, the polymerization reaction and the crosslinking of a rubber phase are completed, and the 29 th section of the cylinder at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 14%, and the notched impact strength was 205J/m.
In this example, compared with example 7, the product obtained by adjusting the shear strength has higher notch impact strength, the same formulation can be used to prepare products with different properties, and if different formulations are used, the range of property adjustment is wider.
Example 10
Continuously adding 5 parts of polybutadiene rubber into a screw rod with the diameter of 65mm and 30 barrel sections from a head feed inlet through a weightless metering scale, wherein the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 30 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer.
The unit is provided with a side feeding system at the 11 th barrel. The side position material extruder is that a screw rod diameter is 65mm, totally 10 section barrels, and the draw ratio is 40: 1 co-rotating twin screw extruder. The screw element combination of the side feeding extruder is subjected to shear reinforcement, and the shear reinforcement is increased by 150mm compared with 45-degree kneading blocks in the front 10 barrel bodies in the main machine. 5 parts of star polybutadiene rubber is added into an extrusion device through a weightless metering scale, a melt is formed at the temperature of between room temperature and 100 ℃, and a pump is continuously added into a fourth section of cylinder body according to the weight ratio of 3: and 30 parts of a mixed liquid of styrene and acrylonitrile of 1. The mixed liquid contains an initiator accounting for 0.1 percent of the mass of the polymerized monomer, a molecular weight regulator accounting for 0.1 percent of the mass of the polymerized monomer and mineral oil accounting for 1 percent of the mass of the polymerized monomer, the materials of the 11 th section of the main screw extrusion equipment enter a main extrusion device after prepolymerization and are mixed with the materials conveyed from the front of the main extrusion equipment, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 250 ℃ after the 18 th section of the cylinder, the polymerization reaction and the crosslinking of a rubber phase are completed, and the 29 th section of the cylinder at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 14%, and the notched impact strength was 225J/m.
The proportions of the monomers and the polymers in the raw materials of examples 8 to 10 were the same, and the rubber phase contents of the obtained ABS resins were all about 14%, but the significant difference in impact strength between the three materials was caused by the difference in the screw shearing capacity and the molecular structure of the monomer polymer. Due to the inherent advantages of the screw extrusion device, the method can conveniently adjust the shear strength of each part by changing the combination of the thread elements, and meets the requirements of different shear strengths in actual production.
In addition, in the method, the raw material polymer is independently added, does not need to be dissolved in a monomer in advance, can conveniently adjust the addition amount of each component through the adjustment of a weight loss metering proportion, can flexibly adjust a formula, and can be switched in the same production line at any time through changing the addition amount of each component to produce products with different performance requirements.
Example 11
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 100 parts of styrene and acrylonitrile mixed liquid of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled between 100 ℃ and 150 ℃ to perform prepolymerization reaction. When the 11 th barrel is reached, another 100 parts of the same mixed monomer solution is continuously added, and the temperature is raised to 120-170 ℃ for polymerization. The temperature of the section 20 of the cylinder body is raised to 200-250 ℃, the polymerization reaction and the crosslinking of the rubber phase are completed, and the section 29 of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 5.5%, and the notched impact strength was 49J/m.
Example 12
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1 at room temperature to 100 ℃, and 80 parts of styrene containing 0.1% of initiator, 0.1% of molecular weight regulator and 1% of mineral oil by mass of the polymerized monomers is continuously added into a fourth section of cylinder through a pump. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 150 ℃ and 250 ℃ after the 18 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the HIPS resin. The rubber phase content of the resin is 12 percent, and the notched Izod impact strength is 33J/m.
Example 13
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 30 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 150 ℃ and 250 ℃ after the 18 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin is 27 percent, and the notch impact strength is 350J/m.
Example 14
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 12 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 150 ℃ and 250 ℃ after the 18 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin is 48%, and the notched impact strength is 330J/m.
Example 15
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 12 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 and 150 ℃ for prepolymerization reaction, 18 parts of SAN resin is added into the 22 th section of the cylinder, the temperature is raised to 150 and 250 ℃, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 29 th section of the cylinder at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 26%, and the notched impact strength was 305J/m.
SAN resin is a copolymer of styrene and acrylonitrile and this example reduces the exothermic heat of polymerization by adding a monomer polymer as a starting material because this heat is already released during the preparation of SAN.
Example 16
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 12 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator, 1 percent of mineral oil and 2 percent of maleic anhydride in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 and 150 ℃ for prepolymerization reaction, 70 parts of PC is added into the 22 th section of the cylinder body in a side feeding mode, the temperature is increased to 240 and 280 ℃, the polymerization reaction and the crosslinking of a rubber phase are completed, the PC and the ABS are blended, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the PC/ABS alloy resin.
Example 17
Continuously adding 10 parts of polybutadiene rubber into a screw from a head feed inlet through a weightless metering scale, wherein the screw has the diameter of 35mm and 15 barrel sections in total, and the length-diameter ratio is 60: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 40 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, the temperature is increased to 240 ℃ after the 12 th section of the cylinder body, the polymerization reaction and the crosslinking of the rubber phase are completed, and the 14 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 22%, the notched impact strength was 295J/m, and the yield was 10 kg per hour.
Example 18
Continuously adding 10 parts of polybutadiene rubber into a screw from a head feed inlet through a weightless metering scale, wherein the screw has the diameter of 35mm and 15 barrel sections in total, and the length-diameter ratio is 60: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 40 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, a plug flow pipeline reaction device with the effective volume of 10 liters is connected in series behind the 10 th section of the cylinder body, the temperature is set to be 150 ℃, the mixture enters a subsequent double-screw extruder after exiting the pipeline, the temperature is increased to 240 ℃ to complete polymerization reaction and rubber phase crosslinking, and the 14 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the ABS resin. The rubber phase content of the resin was 20.5%, the notched impact strength was 285J/m, and the yield was 30 kg per hour.
The formulations of examples 17 and 18 are the same, the screw extruder is the same, the productivity can be enlarged to 3 times by connecting a pipeline reactor in series, and the monomer conversion rate is better, so that the pipeline reactor or the reaction kettle with larger effective volume in series at a proper position can greatly increase the productivity with small investment. Especially, the continuous production can still be realized by adding the plug flow reaction device.
Example 19
10 parts of styrene butadiene rubber are dissolved in 60 parts of 3: 1, adding an initiator accounting for 0.1 percent of the mass of the polymerized monomers, a molecular weight regulator accounting for 0.1 percent of the mass of the polymerized monomers and 1 percent of mineral oil, then adding 3 parts of methyl methacrylate, and forming a uniform solution after 10 hours.
The uniform solution in the previous step is continuously fed into a screw with the diameter of 35mm and 25 sections of barrels, and the length-diameter ratio is 100: 1, reacting 10 sections of cylinders in a co-rotating double-screw extruder unit at the temperature of between room temperature and 120 ℃, gradually heating to 150-240 ℃, completing the polymerization reaction and the crosslinking of rubber phases, and arranging a vacuum devolatilization device at the 24 th section of cylinders at the rear end of an extrusion device. And extruding and granulating to obtain the ABS resin. The content of the rubber phase of the resin is 15 percent, and the notch impact strength is 220J/m.
This example is a conventional feeding method in which a polymer is dissolved first to form a uniform solution and then fed into a device, and it takes 10 hours, and is also applicable to the polymerization method of the present invention, but the efficiency is low.
Example 20
Continuously adding 10 parts of polybutadiene rubber into a screw from a head feed inlet through a weightless metering scale, wherein the screw has the diameter of 35mm and 15 barrel sections in total, and the length-diameter ratio is 60: 1 in the co-rotating twin-screw extruder set, melt is formed at room temperature to 100 ℃, 40 parts of acrylonitrile is continuously added into a fourth section of barrel through a pump, and the temperature of two sections of barrels close to a polymeric monomer adding port does not exceed 150 ℃. The liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil by mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, a plug flow pipeline reaction device with the effective volume of 10 liters is connected in series behind the 10 th section of the cylinder body, the temperature is set to be 150 ℃, the mixture enters a subsequent double-screw extruder after exiting the pipeline, the temperature is increased to 240 ℃ to complete polymerization reaction and rubber phase crosslinking, and the 14 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the NBR resin. The rubber phase content of the resin was 21%, the notched impact strength 245J/m, and the yield 30 kg per hour.
Example 21
10 parts of the butyronitrile rubber are continuously added into a screw rod with the diameter of 35mm and 15 sections of barrels from a head feed inlet through a weightless metering scale, and the length-diameter ratio is 100: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding methyl acrylate and vinyl acetate into a fourth section of cylinder by a pump according to the weight ratio of 3: 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, a plug flow pipeline reaction device with the effective volume of 10 liters is connected in series behind the 10 th section of the cylinder body, the temperature is set to be 150 ℃, the mixture enters a subsequent double-screw extruder after exiting the pipeline, the temperature is increased to 240 ℃ to complete polymerization reaction and rubber phase crosslinking, and the 14 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the resin. The rubber phase content of the resin was 24%, the notched impact strength was 240J/m, and the yield was 30 kg per hour.
Example 22
10 parts of SBS rubber is continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 35mm, 15 sections of barrels are totally arranged, and the length-diameter ratio is 60: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding methyl acrylate and isoprene into a fourth section of a cylinder by a pump in a weight ratio of 3: 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator and 1 percent of mineral oil in the mass of the polymerized monomer. After the materials are added, the temperature is controlled to be between 100 ℃ and 150 ℃ for prepolymerization reaction, a plug flow pipeline reaction device with the effective volume of 10 liters is connected in series behind the 16 th section of the cylinder body, the temperature is set to be 150 ℃, the mixture enters a subsequent double-screw extruder after exiting the pipeline, the temperature is increased to 240 ℃ to complete polymerization reaction and rubber phase crosslinking, and the 24 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the resin. The rubber phase content of the resin was 27%, the notched impact strength was 280J/m, and the yield was 30 kg per hour.
Example 23
10 parts of polybutadiene rubber are continuously added into a screw from a head feed inlet through a weightless metering scale, the diameter of the screw is 65mm, the length-diameter ratio is 120: 1, forming a melt at the temperature of room temperature to 100 ℃, and continuously adding a mixture of 3: 12 parts of mixed liquid of styrene and acrylonitrile of 1, and the temperature of two sections of barrel bodies close to a polymerized monomer feeding port does not exceed 150 ℃. The mixed liquid contains 0.1 percent of initiator, 0.1 percent of molecular weight regulator, 1 percent of mineral oil and 1 percent of maleic anhydride based on the mass of the polymerized monomers. After the materials are added, the temperature is controlled to be between 100 and 150 ℃ for prepolymerization reaction, 50 parts of PC is added into the 22 th section of the cylinder body in a side feeding mode, the temperature is increased to 240 and 280 ℃, the polymerization reaction and the crosslinking of a rubber phase are completed, the PC and the ABS are blended, and the 29 th section of the cylinder body at the rear end of the extrusion device is provided with a vacuum devolatilization device. And extruding and granulating to obtain the PC/ABS alloy resin.
The invention utilizes the advantage of high interface updating efficiency of the screw extrusion device, can improve the heat dissipation efficiency, enables the reaction to be easier to control, has higher efficiency, has the process from feeding to material granulating not more than 2 hours, and has the efficiency obviously superior to the prior continuous bulk method.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (15)

1. A preparation process of a high impact polymer containing conjugated diene monomers is characterized in that the raw materials comprise 10 parts of polymer obtained by polymerizing the conjugated diene monomers and 10-200 parts of polymerized monomer containing carbon-carbon double bonds by weight;
the process comprises the following steps: adding the polymer raw material and the polymerization monomer raw material into a screw extrusion device in proportion, carrying out polymerization reaction and grafting reaction on the raw materials in the screw extrusion device, dispersing polymers of all phases under the shearing action of a screw to form a prepolymer, and continuing polymerization in a subsequent polymerization device to obtain a polymer product.
2. The process for producing a high impact polymer containing conjugated diene monomers according to claim 1, wherein the monomers of the polymer raw material contain not less than 20% by mass of butadiene.
3. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 2, wherein the polymer raw material comprises at least one of polybutadiene rubber, styrene-butadiene rubber, nitrile rubber and SBS rubber.
4. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 1, wherein the weight ratio of the polymer raw material to the polymerized monomers is less than 1: 1.
5. the process for producing a high impact polymer containing a conjugated diene monomer according to claim 1, wherein the temperature of the barrel at two stages near the polymerized monomer feed port of the screw extruder is not more than 150 ℃.
6. The process for preparing a high impact polymer comprising conjugated diene monomers according to claim 1, wherein the subsequent polymerization apparatus is at least one of a screw extrusion apparatus, a pipe reaction apparatus and a reaction vessel.
7. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 6, wherein the subsequent polymerization apparatus comprises a pipe reaction apparatus.
8. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 7, wherein the subsequent polymerization apparatus is a plug flow reaction apparatus and a screw extrusion apparatus connected in series.
9. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 1, wherein the polymer raw material and the polymerization monomer raw material are fed from the front end of the screw extruder.
10. The process for producing a high impact polymer containing a conjugated diene monomer according to claim 9, wherein the polymerization monomer is fed in portions from different portions of a barrel of a screw extruder when the mass ratio of the polymerization monomer to the raw material is more than 80%.
11. The process for preparing high impact polymer containing conjugated diene monomer according to claim 9, wherein the polymer raw material is pre-polymerized in batches and the polymerized monomers are pre-polymerized in screw extrusion devices with different shear strengths, and then are collected in a subsequent polymerization device to complete the subsequent polymerization reaction.
12. The process for preparing a high impact polymer containing a conjugated diene monomer according to claim 1, wherein the overall aspect ratio of the screw extrusion apparatus is not less than 60.
13. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 1, wherein the carbon-carbon double bond polymerized monomer comprises at least one of styrene, acrylonitrile, butadiene, isoprene, vinyl acetate, acrylate and methacrylate.
14. The process for preparing a high impact polymer comprising conjugated diene monomers according to claim 13, wherein the carbon-carbon double bond polymerized monomer is at least one of styrene and acrylonitrile.
15. The process for preparing a high impact polymer containing conjugated diene monomers according to claim 1, wherein the polymer alloy is prepared by feeding other polymers into the screw extruder in a side feeding manner after the prepolymerization is completed.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410659A (en) * 1979-11-07 1983-10-18 The Standard Oil Company Manufacture of rubber modified copolymers in an extruder type reactor
US4463137A (en) * 1982-06-04 1984-07-31 The Standard Oil Company Process for the preparation of rubber-modified thermoplastic resins
US4476283A (en) * 1982-11-12 1984-10-09 Uniroyal, Inc. Graft copolymerization process
CN103030743A (en) * 2012-12-21 2013-04-10 北方华锦化学工业集团有限公司 Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin
CN104558430A (en) * 2015-01-27 2015-04-29 北方华锦化学工业集团有限公司 Method of preparing mass ABS (acrylonitrile-butadiene-styrene) resin with high impact resistance
CN108299601A (en) * 2017-12-12 2018-07-20 北方华锦化学工业股份有限公司 A kind of continuous bulk prepares high flowing, high-impact ABS resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410659A (en) * 1979-11-07 1983-10-18 The Standard Oil Company Manufacture of rubber modified copolymers in an extruder type reactor
US4463137A (en) * 1982-06-04 1984-07-31 The Standard Oil Company Process for the preparation of rubber-modified thermoplastic resins
US4476283A (en) * 1982-11-12 1984-10-09 Uniroyal, Inc. Graft copolymerization process
CN103030743A (en) * 2012-12-21 2013-04-10 北方华锦化学工业集团有限公司 Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin
CN104558430A (en) * 2015-01-27 2015-04-29 北方华锦化学工业集团有限公司 Method of preparing mass ABS (acrylonitrile-butadiene-styrene) resin with high impact resistance
CN108299601A (en) * 2017-12-12 2018-07-20 北方华锦化学工业股份有限公司 A kind of continuous bulk prepares high flowing, high-impact ABS resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
程曾越: "《通用树脂实用技术手册》", 中国石化出版社, pages: 425 - 426 *

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