Wide particle size distribution rubber graft polymer, preparation method and application thereof, latex of wide particle size distribution rubber graft polymer, preparation method of latex, ABS resin and application of ABS resin

Abstract

The invention relates to the field of polymer chemical industry, and discloses a wide particle size distribution rubber graft polymer and a preparation method and application thereof, latex and a preparation method thereof, and ABS resin and application thereof. The core structure material of the rubber graft polymer is rubber, and the shell structure material of the rubber graft polymer is a graft monomer polymer. The particle size of the rubber graft polymer is 0.3-1.5 [mu] m, and the polydispersity coefficient of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.5. According to the wide-particle-size-distribution rubber graft polymer with the core-shell structure, provided by the invention, when a rigid high polymer is toughened, the mechanical property of a product is remarkably improved due to relatively wide distribution of the particle size of a toughened rubber phase.

Description

Technical Field

[0001] This invention relates to the field of polymer chemistry, specifically to rubber-grafted polymers with wide particle size distribution, their preparation methods and applications, their latexes and preparation methods, and ABS resins and their applications. Background Technology

[0002] Core-shell polymers are microparticles with polymer A as the core and polymer B as the outer shell. Both polymer A and polymer B can be produced by homopolymerization of a single monomer or copolymerization of several monomers with different properties. Combining core and shell polymers with different properties can yield a series of latex particles with different functions. Based on the differences in monomer properties, core-shell copolymers can be divided into soft-core-hard-shell and hard-core-soft-shell types. These two types of core-shell polymers are used in toughening brittle materials and exterior wall latex coatings, respectively. Most core-shell polymers are mainly used for toughening brittle materials, such as MBS (methyl methacrylate, butadiene, styrene terpolymer) for toughening PVC and ABS (styrene, acrylonitrile, butadiene terpolymer) for toughening SAN.

[0003] Research on toughening brittle materials with rubber-based elastic materials reveals that the structural parameters of the rubber phase in brittle materials are crucial, including the volume fraction of the rubber phase, its particle size and size distribution, average interparticle spacing, internal morphology of the rubber particles, and interfacial strength between particles and the two phases. Among these, the particle size and size distribution of the rubber phase have the most significant impact on toughening efficiency, and the optimal particle size varies depending on the type of brittle material being toughened. For example, larger rubber particles (1-2 μm in diameter) are most effective for toughening PS, as they can generate voids under relatively weak crack front stress fields. For PA, particles with a diameter of 0.2-0.3 μm are most effective, as their voiding requires a stronger crack front stress field. Increasing the average particle size of the rubber phase from 0.2 μm to 1.0 μm can improve the Izod impact strength of HIPS, but it significantly reduces the Izod impact strength of rubber-toughened PA.

[0004] It is well known that the toughening requirements for particle size in rigid polymers depend on the inherent fracture mechanism of the matrix. Brittle glassy matrices are generally more prone to crazing with large rubber particles (greater than 1 μm). Furthermore, for matrices that can absorb fracture energy through shear yielding, effective toughening can be achieved using modifiers with relatively small particles, on the order of 0.5 μm or smaller. Further research has found that when toughening rigid materials with both fracture mechanisms, if the rubber phase used for toughening can exist in two different particle sizes simultaneously, the product performance can be significantly improved.

[0005] ABS toughened with rubber of a certain particle size exhibits good tensile and impact resistance. When preparing grafted rubber for toughening using the emulsion method, two (or more) rubber particles of different sizes can be used as raw materials. By utilizing the synergistic toughening effect of rubber particles of different sizes, products with high impact strength, high tensile strength, and excellent overall performance can be obtained.

[0006] When producing ABS using the emulsion method, two (or more) toughening rubber particles of different particle sizes are often used to obtain better product performance. The synergistic toughening effect of large and small particle sizes results in products with high impact strength, high tensile strength, and excellent overall performance. To obtain grafted rubber with different particle sizes, graft polymerization is usually performed using rubber latexes of different particle sizes as raw materials. Graft polymerization of rubber latexes of different particle sizes alone followed by blending, or mixing them in a certain proportion before graft polymerization, can prepare grafted rubber with a wide particle size distribution. For example, CN102199253A discloses the method of grafting latex with a particle size of approximately 300 nm and ultra-large particle sizes of 450 nm, 650 nm, and 720 nm to obtain polybutadiene rubber with different particle size distributions. Therefore, an ABS production unit needs to be capable of simultaneously producing latexes of two particle sizes, which is usually achieved by agglomerating small-particle-size rubber latexes into latexes of different particle sizes. However, for production facilities, producing latex of two different particle sizes increases the difficulty of production organization, and for existing production facilities, if they want to produce grafted rubber with a wide particle size, a large amount of capital needs to be invested in production modifications. Summary of the Invention

[0007] The purpose of this invention is to overcome the problem that the particle size of core-shell structured rubber grafted polymers prepared in current processes is limited by the particle size of the rubber latex used, and to provide a rubber grafted polymer with a wide particle size distribution, its preparation method and application, its latex and preparation method, as well as ABS resin and its application.

[0008] To achieve the above objectives, the present invention provides a rubber graft polymer with a core-shell structure and a wide particle size distribution. The core material of the rubber graft polymer is rubber, and the shell material is a grafted monomer polymer. The particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity index of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.5.

[0009] A second aspect of the present invention provides a rubber graft polymer latex with a core-shell structure and a wide particle size distribution. The latex includes the rubber graft polymer with a wide particle size distribution provided by the present invention. In the latex, the particle size of the rubber graft polymer is 0.3-1.5 μm and the polydispersity index of the rubber graft polymer is 0.1-0.5.

[0010] A third aspect of the present invention provides a method for preparing a rubber graft polymer latex with a core-shell structure and a wide particle size distribution, the method comprising the following steps:

[0011] (1) A first grafting reaction is carried out by mixing and contacting the rubber latex, the first grafting monomer, the first chain transfer agent, the electrolyte and the first initiator to achieve a first emulsion polymerization reaction, thereby obtaining the first latex;

[0012] (2) The first latex, the second grafting monomer, the second chain transfer agent, the second emulsifier and the second initiator are mixed and contacted to carry out a second emulsion polymerization reaction to achieve incremental grafting and obtain the second latex;

[0013] (3) The second latex is mixed with the third initiator and aged to obtain a rubber graft polymer latex with a core-shell structure and a wide particle size distribution.

[0014] The fourth aspect of the present invention provides a rubber graft polymer latex with a core-shell structure and a wide particle size distribution prepared by the preparation method described in the present invention.

[0015] The fifth aspect of this invention provides a method for preparing a rubber graft polymer with a core-shell structure and a wide particle size distribution, the method comprising:

[0016] i) Prepare a rubber graft polymer latex with a core-shell structure and a wide particle size distribution according to the method of the present invention;

[0017] ii) The core-shell structured, wide-particle-size rubber graft polymer latex is coagulated, washed, and dried.

[0018] The sixth aspect of the present invention provides a rubber graft polymer with a core-shell structure and a wide particle size distribution, prepared by the preparation method described in the present invention.

[0019] The seventh aspect of the present invention provides the application of the core-shell structured, wide-particle-size rubber graft polymer of the present invention in toughening SAN, PP, PVC and PC / ABS resin materials.

[0020] The eighth aspect of the present invention provides an ABS resin comprising a core-shell structured, wide-particle-size rubber graft polymer and a SAN resin provided by the present invention.

[0021] The ninth aspect of this invention provides the application of the ABS resin described herein in the fields of machinery, electrical engineering, textiles, automobiles, aircraft, and ships.

[0022] The core-shell structure of the rubber graft polymer with a wide particle size distribution provided by this invention can significantly improve the mechanical properties of products when toughening rigid polymers because the toughening rubber phase has a wide particle size distribution, thus taking into account different toughening mechanisms.

[0023] The wide particle size distribution rubber graft polymer provided by this invention has a well-coated "core-shell" structure, which can improve the dispersibility of the rubber graft polymer in the material to be toughened and significantly improve the appearance of "pitting" on the surface of the product.

[0024] In existing technologies for producing core-shell polymers using seed emulsion polymerization, seed latexes with a wide particle size distribution are typically used to obtain a broad particle size distribution. To further broaden the particle size of the grafted latex, seed latexes of different particle sizes are often blended before graft polymerization. Achieving this requires producing latexes with various particle sizes, which complicates the production process. The method for preparing a broad particle size distribution rubber grafted core-shell polymer described in this invention is not limited by the particle size and distribution of the rubber latex used for grafting. Whether using small-particle-size, narrow-distribution rubber latex or large-particle-size, broad-distribution rubber latex, the preparation method provided by this invention can successfully produce a broad particle size distribution rubber grafted polymer with a core-shell structure. Therefore, using the preparation method provided by this invention, there is no need to pre-treat small-particle-size, narrow-distribution rubber latex through agglomeration to obtain broad-distribution grafted rubber latexes with different particle sizes and use them as raw materials for graft polymerization; broad-distribution rubber grafted core-shell polymers can be successfully prepared directly using small-particle-size, narrow-distribution rubber latex as raw material. The method provided by this invention is simple, efficient, easy to operate, and suitable for industrial production.

[0025] This invention significantly increases the particle size and surface area of ​​the core polymer latex particles by adding a certain amount of "shell" monomers that can penetrate into the latex particles during the initial stage of the graft polymerization reaction. Simultaneously, a certain amount of electrolyte is added to bring the latex particles to a critically unstable state, promoting controlled aggregation. As the reaction proceeds, a certain amount of large-particle-size, multi-core polymers are ultimately formed. Furthermore, by controlling the solid content of the polymerization system before and after the reaction, the aggregation of latex particles can be achieved while avoiding the formation of coagulated substances.

[0026] The ABS resin formed by toughening SAN resin with a core-shell structure and a wide particle size distribution of rubber graft polymer provided by this invention has excellent mechanical properties and can significantly improve the impact strength and toughness of the material. It can be widely used in the fields of machinery, electrical, textile, automobile, aircraft and shipbuilding. Detailed Implementation

[0027] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0028] This invention provides a rubber graft polymer with a core-shell structure and a wide particle size distribution. The core material of the rubber graft polymer is rubber, and the shell material is a grafted monomer polymer. The particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity index of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.5.

[0029] According to a preferred embodiment of the present invention, the particle size of the rubber graft polymer is 0.5-1.2 μm, and the polydispersity index of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.3.

[0030] In this invention, the shell / core mass ratio of the rubber grafted polymer can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the shell / core mass ratio of the rubber grafted polymer is 30-60:100, and preferably 40-50:100.

[0031] In this invention, the range of types of rubber that can be selected is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the rubber is one or more of polybutadiene, polybutadiene-styrene, and polybutyl acrylate, preferably one or more of polybutadiene and polybutadiene-styrene.

[0032] In this invention, the range of types of grafted monomer polymers is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the grafted monomer polymer is a copolymer of at least two grafted monomers selected from acrylonitrile, styrene, α-methylstyrene, and methyl methacrylate. According to a preferred embodiment of the invention, the grafted monomer polymer is a copolymer of acrylonitrile and styrene, and the content of either one is not less than 25-30 wt%.

[0033] This invention provides a rubber graft polymer latex with a core-shell structure and a wide particle size distribution. The latex includes the rubber graft polymer with a wide particle size distribution described in this invention. In the latex, the particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity index of the rubber graft polymer is 0.1-0.5.

[0034] According to a preferred embodiment of the present invention, in the wide particle size distribution rubber graft polymer latex, the particle size of the rubber graft polymer is 0.5-1.2 μm, and the polydispersity index of the rubber graft polymer is 0.1-0.3.

[0035] In this invention, the solid content of the wide particle size distribution rubber grafted polymer latex can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solid content of the wide particle size distribution rubber grafted polymer latex is 35-48 wt%, preferably 38-45 wt%.

[0036] All rubber grafted polymer latexes with a core-shell structure and wide particle size distribution possessing the aforementioned characteristics can achieve the objectives of this invention. There are no special requirements for their preparation methods. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the preparation method of the rubber grafted polymer latex with a core-shell structure and wide particle size distribution includes the following steps:

[0037] (1) A first grafting reaction is carried out by mixing and contacting the rubber latex, the first grafting monomer, the first chain transfer agent, the electrolyte and the first initiator to achieve a first emulsion polymerization reaction, thereby obtaining the first latex;

[0038] (2) The first latex, the second grafting monomer, the second chain transfer agent, the second emulsifier and the second initiator are mixed and contacted to carry out a second emulsion polymerization reaction to achieve incremental grafting and obtain the second latex;

[0039] (3) The second latex is mixed with the third initiator and aged to obtain a rubber graft polymer latex with a core-shell structure and a wide particle size distribution.

[0040] In this invention, the range of types of rubber latex is relatively wide, and commonly used rubbers can be used in this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the rubber latex is selected from one or more of polybutadiene latex, polybutadiene-styrene latex, and polybutyl acrylate latex.

[0041] In this invention, the solid content of the rubber latex can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solid content of the rubber latex is 40-60 wt%.

[0042] In this invention, the particle size of the rubber latex particles in the rubber emulsion can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the particle size of the rubber latex particles in the rubber emulsion is 100-800 nm.

[0043] In this invention, the polydispersity coefficient of the rubber latex particles in the rubber emulsion can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the polydispersity coefficient of the rubber latex particles in the rubber emulsion is 0.01-0.05.

[0044] In existing technologies for producing core-shell polymers using seed emulsion polymerization, seed latexes with a wide particle size distribution are typically used to obtain a broad particle size distribution. To further broaden the particle size of the grafted latex, seed latexes of different particle sizes are often blended before graft polymerization. Achieving this requires producing latexes with various particle sizes, which complicates the production process. The method for preparing a broad particle size distribution rubber grafted core-shell polymer described in this invention is not limited by the particle size and distribution of the rubber latex used for grafting. Whether using small-particle-size, narrow-distribution rubber latex or large-particle-size, wide-distribution rubber latex, the preparation method provided by this invention can successfully produce a broad particle size distribution rubber grafted polymer with a core-shell structure. Therefore, the preparation method provided by this invention eliminates the need for prior agglomeration or other treatments to obtain grafted rubber latex with different particle sizes and a wide distribution, which can then be used as raw material for graft polymerization. Wide particle size distribution rubber grafted core-shell polymers can be successfully prepared directly using small particle size, narrow distribution grafted rubber latex as raw material. The method provided by this invention is simple, efficient, easy to operate, and suitable for industrial production.

[0045] In this invention, the ratio of electrolyte to dry rubber emulsion in step (1) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the amount of electrolyte added in step (1) is 0.02-0.25 wt% of the dry rubber emulsion, preferably 0.08-0.2 wt%.

[0046] By adopting the aforementioned preferred scheme, adding a certain amount of electrolyte in the early stage of the graft polymerization reaction can put the latex particles in a critically unstable state, promote the controllable "aggregation" of the latex particles, and eventually form a certain amount of polymer with a large particle size "multi-core" structure as the reaction proceeds.

[0047] In this invention, the ratio of the first grafted monomer to the dry base of the rubber latex in step (1) can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the amount of the first grafted monomer in step (1) accounts for 10-100 wt% of the dry base of the rubber latex, preferably 15-30 wt%.

[0048] In this invention, there are no special requirements for the type of electrolyte; commonly used electrolytes can achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the electrolyte is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium chloride, and ammonium chloride. Preferably, the electrolyte in which the cation is different from the cation in the emulsifier is an electrolyte. For example, when potassium disproportionated rosinate solution is used as the emulsifier, the electrolyte is not preferably an electrolyte with potassium ions as the cation, such as potassium carbonate or potassium bicarbonate.

[0049] Using the aforementioned preferred electrolyte can reduce the precipitation of emulsifier in the aqueous polymerization phase to a certain extent, and can avoid the excessive formation of monomer compatibilizing micelles and monomer droplets, thereby reducing the grafting rate of shell monomers and affecting the grafting effect.

[0050] According to a preferred embodiment of the present invention, the theoretical solid content of the first latex after step (1) is 35-48 wt%, preferably 38-45 wt%.

[0051] According to a preferred embodiment of the present invention, after step (2), the solid content of the second latex is 38-45 wt%, preferably 38-42 wt%.

[0052] According to a preferred embodiment of the present invention, after step (3), the solid content of the wide particle size distribution rubber graft polymer latex is 38-45 wt%, preferably 38-43 wt%.

[0053] In this invention, the ratio of graft monomer to dry rubber emulsion can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the total amount of the first graft monomer and the second graft monomer added is 50-150 wt% of the dry rubber emulsion, preferably 60-70 wt%.

[0054] By adopting the aforementioned preferred scheme, adding a certain amount of "shell" monomers that can enter the latex particles in the early stage of the graft polymerization reaction can significantly increase the particle size and surface area of ​​the "core" polymer latex particles.

[0055] In this invention, the ratio of chain transfer agent to dry rubber emulsion can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the total amount of the first chain transfer agent and the second chain transfer agent added is 0.18-1.8 wt% of the dry rubber emulsion, preferably 0.4-0.8 wt%; the amount of the first chain transfer agent accounts for 30-90 wt% of the total amount of chain transfer agent, preferably 50-80 wt%.

[0056] In this invention, the ratio of initiator to dry rubber emulsion can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the total amount of the first initiator, the second initiator and the third initiator added is 0.16-1.6 wt% of the dry rubber emulsion, preferably 0.5-0.8 wt%.

[0057] According to a preferred embodiment of the present invention, the first initiator accounts for 10-40 wt% of the total amount of initiator, preferably 14-22 wt%; the second initiator accounts for 40-70 wt% of the total amount of initiator, preferably 50-70 wt%; and the third initiator accounts for 10-40 wt% of the total amount of initiator, preferably 20-30 wt%.

[0058] In this invention, the ratio of the second emulsifier to the dry basis of the rubber latex can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the total amount of the second emulsifier added is 0.16-1.6 wt% of the dry basis of the rubber latex, preferably 0.2-0.5 wt%.

[0059] In this invention, the range of grafting monomers that can be selected is relatively wide, and commonly used grafting monomers can be applied to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the first grafting monomer and the second grafting monomer are each independently selected from one or more of acrylonitrile, styrene, α-methylstyrene and methyl methacrylate.

[0060] In this invention, there are no special requirements for the type of chain transfer agent. Any chain transfer agent that can achieve the purpose of this invention is applicable to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the first chain transfer agent and the second chain transfer agent are each independently selected from one or more of tert-dodecyl mercaptan and n-dodecyl mercaptan.

[0061] In this invention, there are no special requirements for the type of initiator; commonly used initiators are all applicable to this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the first initiator, the second initiator, and the third initiator are each independently selected from one or more of tert-butyl hydroperoxide, cumene hydroperoxide, p-menthol hydroperoxide, methylcyclohexane hydroperoxide, p-methyl cumene hydroperoxide, cumene, and tetrahydronaphthalene hydroperoxide.

[0062] In this invention, there are no special requirements for the type of the second emulsifier. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the first emulsifier and the second emulsifier are each independently selected from one or more anionic emulsifiers.

[0063] According to a preferred embodiment of the present invention, the first grafting monomer and the second grafting monomer are each independently selected from at least two of acrylonitrile, styrene, α-methylstyrene, and methyl methacrylate, and the content of any one thereof is not less than 25-30 wt%. Preferably, the first grafting monomer and the second grafting monomer are each independently selected from a mixture of acrylonitrile and styrene, and the content of any one thereof is not less than 25-30 wt%.

[0064] In this invention, the type of the second grafting monomer is the same as or different from that of the first grafting monomer; when the type of the second grafting monomer is the same as that of the first grafting monomer, the composition of the second grafting monomer is different from that of the first grafting monomer.

[0065] According to a preferred embodiment of the present invention, the anionic emulsifier is selected from one or more of potassium fatty acid, potassium oleate, potassium disproportionated rosinate, sodium dodecyl sulfonate, and sodium butylnaphthalene sulfonate.

[0066] In this invention, the temperature range of the first emulsion polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the temperature of the first emulsion polymerization reaction is 35-60°C, for example, it can be 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, etc.

[0067] In this invention, the time range of the first emulsion polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the time of the first emulsion polymerization reaction is 50-70 min, for example, 50 min, 55 min, 60 min, 65 min, 70 min, etc.

[0068] In this invention, the amount of rinsing water used in the first emulsion polymerization reaction can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the amount of rinsing water used in the first emulsion polymerization reaction is 10-150 wt% of the dry basis of the rubber emulsion, preferably 10-80 wt% of the dry basis of the rubber emulsion.

[0069] In this invention, electrolyte may or may not be added in step (2). The role of electrolyte in this invention is mainly reflected in step (1). Therefore, under the condition that the requirement for the amount of electrolyte added in step (1) is met, adding a small amount of electrolyte in step (2) can also achieve good results.

[0070] In this invention, the temperature range of the second emulsion polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the temperature of the second emulsion polymerization reaction is 50-80°C, for example, it can be 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.

[0071] In this invention, the time range of the second emulsion polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the time of the second emulsion polymerization reaction is 100-120 min, for example, 105 min, 110 min, 115 min, 120 min, etc.

[0072] In this invention, the amount of rinsing water used in the second emulsion polymerization reaction can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the amount of rinsing water used in the second emulsion polymerization reaction is 35-135 wt% of the dry basis of the rubber emulsion, preferably 35-100 wt% of the dry basis of the rubber emulsion.

[0073] By adopting the aforementioned preferred scheme, the solid content of the polymerization system before and after the reaction is controlled, so that the latex particles "aggregate" and eventually form a certain amount of polymer with a large particle size "multi-core" structure as the reaction proceeds, while avoiding the formation of solids.

[0074] In this invention, the aging reaction temperature can be selected over a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the aging reaction temperature is 60-80°C, for example, it can be 60°C, 65°C, 70°C, 75°C, 80°C, etc.

[0075] In this invention, the aging reaction time can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the aging reaction time is 15-30 minutes, for example, 15 minutes, 20 minutes, 25 minutes, 30 minutes, etc.

[0076] In this invention, the mixture of the second grafting monomer and the second chain transfer agent, the rinsing water, and the second emulsifier in step (2) are added simultaneously or asynchronously; preferably, when added simultaneously, the mixture of the second grafting monomer and the second chain transfer agent is mixed with the rinsing water and then added continuously with the second emulsifier.

[0077] In this invention, the second initiator is added alone or mixed with the second emulsifier in step (2).

[0078] According to a preferred embodiment of the present invention, the preparation method of the core-shell structure wide particle size distribution rubber graft polymer latex of the present invention further includes: step (1) being carried out in the presence of a first emulsifier.

[0079] In this invention, the ratio of the first emulsifier to the dry basis of the rubber latex can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the amount of the first emulsifier is less than 1 wt% of the dry basis of the rubber latex, preferably less than 0.5 wt%.

[0080] In this invention, there are no special requirements for the type of the first emulsifier. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the first emulsifier is selected from one or more anionic emulsifiers.

[0081] According to a preferred embodiment of the present invention, the anionic emulsifier is selected from one or more of potassium fatty acid, potassium oleate, potassium disproportionated rosinate, sodium dodecyl sulfonate, and sodium butylnaphthalene sulfonate.

[0082] This invention provides a method for preparing a core-shell structured, wide-particle-size-distribution rubber grafted polymer latex, as described in this invention.

[0083] In this invention, the particle size of the rubber graft polymer in the latex of the core-shell structured wide particle size distribution rubber graft polymer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the particle size of the rubber graft polymer in the latex of the core-shell structured wide particle size distribution rubber graft polymer is 0.3-1.5 μm, preferably 0.5-1.2 μm.

[0084] In this invention, the polydispersity coefficient of the rubber graft polymer in the latex of the wide particle size distribution rubber graft polymer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the polydispersity coefficient of the rubber graft polymer in the latex of the wide particle size distribution rubber graft polymer is 0.1-0.5, preferably 0.1-0.3.

[0085] In this invention, the solid content of the wide particle size distribution rubber grafted polymer latex can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solid content of the wide particle size distribution rubber grafted polymer latex is 35-48 wt%, preferably 38-45 wt%.

[0086] All rubber graft polymers with a core-shell structure and wide particle size distribution possessing the aforementioned characteristics can achieve the objectives of this invention. There are no special requirements for their preparation methods. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the preparation method of the rubber graft polymer with a core-shell structure and wide particle size distribution includes:

[0087] i) Prepare a rubber graft polymer latex with a core-shell structure and a wide particle size distribution according to the method of the present invention;

[0088] ii) The core-shell structured, wide-particle-size rubber graft polymer latex is coagulated, washed, and dried.

[0089] This invention provides a rubber graft polymer with a core-shell structure and a wide particle size distribution, prepared by the preparation method described herein. The core structure material of the rubber graft polymer is rubber, and the shell structure material is a grafted monomer polymer. The particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity index of the rubber graft polymer in latex is 0.1-0.5.

[0090] According to a preferred embodiment of the present invention, the particle size of the rubber graft polymer is 0.5-1.2 μm.

[0091] According to a preferred embodiment of the present invention, the polydispersity index of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.3.

[0092] In this invention, the shell / core mass ratio of the rubber grafted polymer can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the shell / core mass ratio of the rubber grafted polymer is 30-60:100, preferably 40-50:100.

[0093] In this invention, when the emulsion polymerization process uses a redox system, an appropriate amount of activator can be added. Commonly used activators are all applicable to this invention. For example, glucose, sodium pyrophosphate and ferrous sulfate can be used as activators. The amount of activator added can be 0.05-1 wt% of the dry basis of the rubber emulsion.

[0094] The core-shell structure-based rubber graft polymer provided by this invention, when used to toughen rigid polymers, can take into account different toughening mechanisms due to the wide particle size distribution of the toughening rubber phase, thereby significantly improving the mechanical properties of the product.

[0095] This invention provides the application of the core-shell structured, wide-particle-size rubber graft polymer described herein in toughening SAN, PP, PVC, and PC / ABS resin materials. The graft polymer described herein can significantly improve the impact strength and toughness of SAN, PP, PVC, and PC / ABS resin materials when toughening them.

[0096] The present invention provides an ABS resin, wherein the ABS resin comprises a core-shell structured, wide-particle-size rubber graft polymer and a SAN resin provided by the present invention.

[0097] In this invention, the ABS resin possesses excellent mechanical properties. According to a preferred embodiment of this invention, the impact strength of the ABS resin is 20-25 kJ / m². 2 The tensile strength is 40-45 MPa, the elongation at break is 22-35%, the flexural strength is 65-71 MPa, and the flexural modulus is 2200-2400.

[0098] In this invention, the mass ratio of the wide particle size distribution rubber graft polymer to the SAN resin in the ABS resin can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the mass ratio of the wide particle size distribution rubber graft polymer to the SAN resin in the ABS resin is 0.25-0.35:1.

[0099] This invention provides the application of the ABS resin described herein in the fields of machinery, electrical engineering, textiles, automobiles, aircraft, and ships.

[0100] In this invention, the methods for testing and evaluating the particle size and polydispersity index of the rubber grafted polymer in the rubber grafted polymer latex, the coagulant content, shell / core ratio, shell monomer utilization rate, and the mechanical properties of ABS products are as follows:

[0101] 1. Test method for particle size and polydispersity index of rubber graft polymer in rubber graft polymer latex (scattering method)

[0102] (1) After the solution to be tested is centrifuged or filtered, the sample with a volume concentration ≤0.5% is added to the cuvette, and the measurement time is set to 1-2 min each time. The test is repeated 5 times.

[0103] (2) After the measurement is completed, record the effective diameter and polydispersity index of the particles.

[0104] 2. Coagulant content in rubber graft polymer latex

[0105] (1) Clean the 120-mesh stainless steel filter screen with deionized water and dry it in an oven at 120℃ until it reaches constant weight, which is recorded as M0;

[0106] (2) Filter grafted latex of mass M1 using a stainless steel filter screen dried to constant weight. Rinse the filter residue with demineralized water until the rinse water becomes clear;

[0107] (3) Place the cleaned filter residue and filter screen together in an oven at 120°C and dry until constant weight, which is recorded as M2;

[0108] (4) Calculate the coagulated content in the latex according to the following formula (1);

[0109]

[0110] 3. Test methods for rubber monomer grafting amount and shell monomer utilization rate

[0111] Weigh out a certain amount of core-shell polymer powder (taking ABS high-resin powder as an example) and record it as m. g0 The solution was dissolved in acetone in a special test tube, shaken for 24 hours, and then separated using a centrifuge at 10000 r / min for 0.5 hours. After centrifugation, the supernatant in the test tube was poured off, and an appropriate amount of acetone was added to repeat the experiment. The final precipitate was a core-shell polymer. The precipitate was dried to constant weight and then weighed, expressed as m. g1 The shell / core ratio of the core-shell polymer is calculated by formula (2) based on the content of the core polymer in the core-shell polymer powder.

[0112]

[0113] in:

[0114] GD% — Percentage of shell polymer to core polymer by weight, wt%.

[0115] m g0 —Weigh the rubber graft powder, in grams;

[0116] m g1 —The weight of the product obtained after centrifugation and drying, in grams;

[0117] A% — Content of the core polymer in the rubber graft powder, in wt%.

[0118] The shell utilization rate of the shell unit is calculated using formula (3).

[0119]

[0120] in:

[0121] GE% — The percentage of monomers forming the core-shell polymer relative to the total shell monomers, in wt%.

[0122] m g0 —Weigh the rubber graft powder, in grams;

[0123] m g1 —The weight of the product obtained after centrifugation and drying, in grams;

[0124] A% — Content of the core polymer in the rubber graft powder, in wt%.

[0125] 4. Preparation of test strips for ABS products and evaluation methods for various properties.

[0126] Rubber grafted polymer powder was blended with acrylonitrile-styrene copolymer (SAN resin, commercially available product of China Petroleum Jilin Petrochemical Company with brand name 2437) at a weight ratio of 25 / 75 and granulated. The mechanical properties of the ABS product were tested according to the method specified in the table below.

[0127]

[0128] Example 1

[0129] (1) Core-shell polymerization was carried out on polybutadiene (PB) latex with a content of 56.25%, a particle size of 0.314 μm, and a polydispersity index of 0.022 to form a core-shell polymer with PB as the "core" and polyacrylonitrile-styrene copolymer as the "shell". 3200 kg of PB latex, 300 kg of monomer composed of acrylonitrile (AN) and styrene (St) (acrylonitrile to styrene weight ratio of 28:72), 5.37 kg of chain transfer agent tert-dodecyl mercaptan (TDDM), 915.2 kg of rinsing water, 1.8 kg of sodium carbonate, 210 kg of activator (solid content: 5.23 wt%), and 306 kg of emulsifier solution (potassium disproportionated rosinate solution, solid content: 1.96 wt%) were added to the reactor. Hot water was introduced into the jacket of the reactor to raise the temperature of the material inside the reactor to 40°C. 2.06 kg of initiator cumene hydroperoxide (CHP) was added to start the reaction. The theoretical solid content of the polymerization system after all monomers have completely reacted at this stage is 43.0 wt%.

[0130] (2) Sixty minutes after the start of the reaction, an incremental reaction was initiated. 306 kg of emulsifier solution (potassium disproportionated rosinate solution, solid content: 1.96 wt%), 900 kg of a mixed monomer consisting of acrylonitrile (AN) and styrene (St) (acrylonitrile to styrene weight ratio 28:72), 3.63 kg of TDDM, and 1370.4 kg of rinsing water were mixed. These materials were continuously added to the reactor at a constant flow rate over 120 minutes. Simultaneously, 8.25 kg of initiator CHP was added to the reactor at a constant flow rate over the same period, allowing for an incremental reaction lasting 120 minutes. As the incremental reaction progressed, the temperature inside the reactor gradually increased to 76–77 °C. At the end of this stage, the solid content in the polymerization system was 39.5 wt%.

[0131] (3) After the incremental reaction is completed, 3.19 kg of initiator CHP and 87 kg of activator (solid content: 5.23 wt%) are added for aging reaction. After aging for 20 min, the material is cooled to 60°C and unloaded. The latex solid content is 39.8 wt%.

[0132] (4) After the latex is cooled, the polymer latex is demulsified using an acidic coagulant, washed, dehydrated and dried, the "shell / core" of the powder is tested and the "shell" monomer utilization rate is calculated. After the powder is blended and granulated with SAN, the particle size of the rubber phase in the particles and the mechanical properties of the product are tested.

[0133] Example 2

[0134] The operation steps are the same as in Example 1, except that in step (1), 384 kg of mixed monomers (acrylonitrile to styrene weight ratio of 28:72), 8.59 kg of TDDM, and 1033.56 kg of rinsing water are added; the material in the reactor is heated to 40°C, and 2.64 kg of initiator cumene hydroperoxide (CHP) is added to start the reaction; the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%; in step (2), 816 kg of mixed monomers, 3.29 kg of TDDM, and 1251.05 kg of rinsing water are added; the amount of initiator CHP used in step (2) is 7.48 kg. After the reaction in step (2) is completed, the solid content of the polymerization system is 39.5 wt%. After the reaction in step (3) is completed, the solid content of the latex is 39.8 wt%.

[0135] Example 3

[0136] The operating steps are the same as in Example 2, except that in step (1), the amount of rinsing water is reduced from 1033.56 kg to 798.9 kg; at the end of the reaction in step (1), the theoretical solid content of the polymerization system after all monomers have completely reacted is 45.0 wt%; in step (2), the amount of rinsing water is increased from 801.06 kg to 1492.8 kg. After the reaction in step (2), the solid content of the polymerization system is 39.5 wt%. At the end of the reaction in step (3), the solid content of the latex is 39.7 wt%.

[0137] Example 4

[0138] The operating steps are the same as in Example 2, except that the amount of rinsing water in step (2) is reduced from 1251.05 kg to 802.6 kg. After the reaction in step (2) is complete, the solid content in the polymerization system is 42.5 wt%. At the end of the reaction in step (3), the latex solid content is 42.7 wt%.

[0139] Example 5

[0140] The operating steps are the same as in Example 2, except that 3.6 kg of sodium carbonate and 1042.5 kg of rinsing water are added in step (1); the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%. The solid content of the polymerization system after the reaction is completed in step (2) is 39.5 wt%. The solid content of the latex is 39.8 wt% after the reaction is completed in step (3).

[0141] Example 6

[0142] The operating steps are the same as in Example 2, except that in step (1), 2.34 kg of potassium carbonate is added instead of 1.8 kg of sodium carbonate. The theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.1 wt%. In step (2), the solid content of the polymerization system after the reaction is complete is 39.5 wt%. In step (3), the latex solid content is 39.8 wt% at the end of the reaction.

[0143] Example 7

[0144] The operation steps are the same as in Example 1, except that in step (1), styrene-butadiene latex with a content of 46.25 wt%, a particle size of 0.454 μm, and a polydispersity index of 0.032 is used instead of polybutadiene latex for polymerization, and a mixed emulsifier composed of potassium fatty acid and sodium dodecyl sulfonate (solid content: 2.12 wt%, weight ratio of potassium fatty acid to sodium dodecyl sulfonate: 7.5:1) is used instead of potassium disproportionate emulsifier used in the polymerization reaction; in step (1), 3892 kg of styrene-butadiene latex, 280 kg of mixed emulsifier composed of potassium fatty acid and sodium dodecyl sulfonate, and 223.3 kg of rinsing water are added; the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%; in step (2), 280 kg of mixed emulsifier composed of potassium fatty acid and sodium dodecyl sulfonate is added. After the reaction in step (2) is completed, the solid content of the polymerization system is 39.5 wt%. At the end of the reaction in step (3), the latex solid content was 39.8 wt%.

[0145] Example 8

[0146] The operating steps are the same as in Example 2, except that 1.5 kg of sodium carbonate is added in step (1) and 0.3 kg of sodium carbonate is added in step (2). The theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%. The solid content of the polymerization system after the reaction in step (2) is 39.5 wt%. The latex solid content at the end of the reaction in step (3) is 39.7 wt%.

[0147] Example 9

[0148] The operation steps are the same as in Example 1, except that 0.9 kg of sodium carbonate is added in step (1); the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%. After the reaction in step (2) is completed, the solid content of the polymerization system is 39.5 wt%. After the reaction in step (3) is completed, the solid content of the latex is 39.8 wt%.

[0149] Example 10

[0150] The operating steps are the same as in Example 1, except that in step (1), the amount of rinsing water added is 2042.36 kg; the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 35.0 wt%. In step (2), the amount of rinsing water added is 223.86 kg. After the reaction in step (2) is completed, the solid content of the polymerization system is 39.5 wt%. At the end of the reaction in step (3), the solid content of the latex is 39.8 wt%.

[0151] Example 11

[0152] The operating steps are the same as in Example 1, except that in step (1), 180 kg of mixed monomers (acrylonitrile to styrene weight ratio of 28:72) and 759.21 kg of rinsing water are added; the theoretical solid content of the polymerization system after all monomers have completely reacted in this stage is 43.0 wt%. In step (2), 1022 kg of mixed monomers (acrylonitrile to styrene weight ratio of 28:72) and 1515.65 kg of rinsing water are added. The amount of rinsing water added in step (2) is 223.86 kg. After the reaction in step (2) is completed, the solid content of the polymerization system is 39.5%. At the end of the reaction in step (3), the latex solid content is 39.8 wt%.

[0153] Comparative Example 1

[0154] The operation steps are the same as in Example 1, except that sodium carbonate is not added in step (1).

[0155] Comparative Example 2

[0156] The operation steps are the same as in Example 2, except that sodium carbonate is not added in step (1).

[0157] Comparative Example 3

[0158] The operation steps are the same as in Example 3, except that sodium carbonate is not added in step (1).

[0159] Comparative Example 4

[0160] The operation steps are the same as in Example 7, except that sodium carbonate is not added in step (1).

[0161] The particle size and polydispersity index of the rubber-grafted polymer in the latex of the test examples and comparative examples are shown in Table 1.

[0162] Table 1. Particle size and polydispersity index of rubber-grafted polymers in rubber-grafted polymer latex.

[0163]

[0164] The coagulant content in the rubber grafted polymer latex of the test examples and comparative examples, as well as the GD% and GE% of each powder after drying, are shown in Table 2.

[0165] Table 2. Rubber grafting polymer latex coagulant content, rubber grafting amount, and monomer grafting efficiency.

[0166] Test Project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Concrete content / % 0.177 0.192 0.202 0.373 0.235 0.252 GD% 46.20 45.22 43.35 42.78 40.07 42.04 GE% 69.30 67.83 65.03 64.17 60.11 63.06 Test Project Example 7 Example 8 Example 9 Example 10 Example 11 Concrete content / % 0.211 0.185 0.16 0.12 0.17 GD% 40.06 45.88 47.02 47.05 48.10 GE% 60.09 68.82 71.11 71.05 71.03 Test Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Concrete content / % 0.36 0.118 0.126 0.145 GD% 47.36 45.70 44.73 44.98 GE% 71.04 68.55 67.10 67.47

[0167] Table 3 Mechanical Properties of ABS Products

[0168]

[0169]

[0170] As can be seen from Tables 1 and 2, in the initial stage of the graft polymerization reaction, increasing the amount of "shell" monomer, appropriately reducing the solid content of the polymerization system, and adding a small amount of electrolyte can bring the latex particles to a critically unstable state, causing the latex particles to "aggregate" to a certain extent. As the reaction proceeds, a certain amount of large-sized "multi-core" core-shell structure polymers are eventually formed, which increases the particle size and polydispersity index of the latex.

[0171] Increasing the amount of electrolyte in the polymerization system can cause the emulsifier dissolved in water to precipitate out to some extent, leading to an increase in the amount of emulsifier forming compatibilizing micelles and monomer droplets. However, by reducing the amount of emulsifier used in the primary reaction stage, the emulsifier concentration in the polymerization system can still be maintained at a low level. Under these circumstances, by increasing the ionic strength of the system, the double electron layer of the latex particles becomes thinner, the resistance to monomer entering the latex particles decreases, and the amount of "core" polymer grafting increases significantly.

[0172] Comparing Examples 1, 2, and 3 with Comparative Examples 1, 2, and 3, it can be seen that adding a small amount of electrolyte in the first reaction stage can reduce the stability of the polymerization system and produce a large number of "polynuclear" rubber graft polymers. This increases the latex particle size from 0.352–0.364 μm, 0.464–0.487 μm, and 0.483–0.508 μm to 0.785–0.813 μm, 1.077–1.212 μm, and 1.546–1.583 μm, respectively, and the polydispersity index from 0.045–0.058, 0.066–0.075, and 0.065–0.068 to 0.157–0.169, 0.192–0.209, and 0.210–0.237.

[0173] Comparing Examples 1-3 and Comparative Examples 1-3, it can be seen that when an electrolyte is added in the primary reaction stage of graft polymerization, increasing the amount of primary monomer when the primary reaction solid content is relatively high, or increasing the primary reaction solid content without increasing the amount of monomer, can increase the probability of latex particle collision and obtain large-particle-size "multi-core" graft polymers, thereby increasing the particle size of the graft polymers in the latex and increasing the polydispersity index.

[0174] Meanwhile, with the increase of solid content in the primary reaction, the amount of free emulsifier in the polymerization system increases significantly, leading to an increase in the formation of free SAN in this reaction stage. This trend is even more pronounced when additional electrolytes are added and the amount of primary reaction monomers is increased, resulting in a decrease in rubber grafting rate and grafting monomer utilization.

[0175] Comparing Examples 2 and 5, it can be seen that the content of coagulated material in the latex increases significantly with the increase of electrolyte dosage. Simultaneously, due to the decrease in latex stability, the rubber grafting rate and the utilization rate of grafting monomers decrease.

[0176] Comparing Examples 2, 3, and 4, it can be seen that when the total solid content of the graft polymerization system remained unchanged, the coagulated content in the latex did not increase significantly. However, when the final solid content of the polymerization system was increased by reducing the amount of rinsing water used in the incremental stage, the coagulated content in the grafted latex increased significantly.

[0177] Comparing Examples 1 and 6, it can be seen that replacing sodium carbonate with equimolar potassium carbonate causes more disproportionated rosinate potassium, which was originally dissolved in the aqueous phase, to precipitate, leading to an increase in the formation of monomer toughening micelles and monomer droplets. This ultimately results in a significant decrease in the rubber grafting rate and monomer grafting efficiency. As the rubber grafting rate decreases, the dispersion performance of the rubber-grafted polymer in ABS declines, ultimately reducing the mechanical properties of the material.

[0178] As can be seen from Example 7 and Comparative Example 4, the preparation method provided by the present invention is not only applicable to polybutadiene latex with a particle size of 0.28-0.35 μm and a polydispersity index of 0.02-0.03, but also applicable to styrene-butadiene latex with a particle size of 0.40-0.60 μm and a polydispersity index of 0.03-0.05.

[0179] Comparative Examples 2 and 8 show that, while meeting the electrolyte addition amount in step (1), adding a small amount of electrolyte in step (2) can also achieve good results in increasing particle size and polydispersity index.

[0180] As can be seen from Tables 1 and 3, compared with Comparative Examples 1-4, Examples 1-5 and 7 significantly improved the particle size and polydispersity index of the rubber graft polymer in the grafted emulsion by adjusting the amount of monomer in the primary reaction, the solid content, and using a certain amount of electrolyte. At this time, the mechanical properties of the product were significantly improved, with increased impact strength, tensile strength, and elongation at break. With a tensile strength not less than 43.0 MPa, the impact strength exceeded 22 kJ / m². 2 The highest value reached 23.83 kJ / m 2 The tensile elongation at break exceeds 26%, reaching a maximum of 32.8%.

[0181] As can be seen from the above examples and comparative examples, this invention utilizes the initial addition of a portion of the required "shell" monomers during the graft polymerization reaction to significantly increase the particle size and surface area of ​​the "core" polymer. By controlling the solid content and emulsifier concentration of the polymerization system and adding a certain amount of electrolyte, the latex particles are brought to a critically unstable state, promoting a certain degree of "agglomeration" of the latex particles at this stage. As the reaction proceeds, the "agglomerated" latex particles eventually form a large-particle-size "multi-core" core-shell structure polymer. When using the core-shell polymer prepared by this method to toughen rigid polymers, different particle sizes of toughened rubber can achieve different toughening mechanisms, significantly improving the mechanical properties of ABS products.

[0182] The preferred embodiments of the present invention have been described above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A rubber graft polymer having a core-shell structure with a broad particle size distribution, characterized in that, The core structure material of the rubber graft polymer is rubber, and the shell structure material is graft monomer polymer; the particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity coefficient of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.

5.

2. The wide particle size distribution rubber graft polymer according to claim 1, wherein, the particle size of the rubber graft polymer is 0.5-1.2 μm; and / or the polydispersity coefficient of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.3; and / or the "shell / core" mass ratio of the rubber graft polymer is 30-60:

100.

3. The wide particle size distribution rubber graft polymer according to claim 2, wherein, the "shell / core" mass ratio of the rubber graft polymer is 40-50:

100.

4. The wide particle size distribution rubber graft polymer according to claim 1, wherein, the rubber is one or more of polybutadiene, polybutadiene-styrene, and polybutyl acrylate; and / or the graft monomer polymer is a copolymer of at least two graft monomers selected from acrylonitrile, styrene, α-methylstyrene, and methyl methacrylate.

5. The wide particle size distribution rubber graft polymer according to claim 4, wherein, the rubber is one or more of polybutadiene and polybutadiene-styrene; and / or the graft monomer polymer is a copolymer of acrylonitrile and styrene, and the content of any one of them is not less than 25-30 wt%.

6. A wide particle size distribution rubber graft polymer latex having a core-shell structure, characterized in that, The latex comprises the wide particle size distribution rubber graft polymer according to any one of claims 1-5, and the particle size of the rubber graft polymer in the latex is 0.3-1.5 μm, and the polydispersity coefficient of the rubber graft polymer is 0.1-0.

5.

7. The wide particle size distribution rubber graft polymer latex of claim 6, wherein the rubber graft polymer latex has a particle size distribution of 0.1 to 0.5 μm. The particle size of the rubber graft polymer in the latex is 0.5-1.2 μm, and the polydispersity coefficient of the rubber graft polymer is 0.1-0.3; and / or The solid content of the latex is 35-48 wt%.

8. A process for the preparation of a wide particle size distribution rubber graft polymer latex having a core-shell structure, characterized in that, The method comprises the following steps: (1) mixing and contacting a rubber emulsion, a first graft monomer, a first chain transfer agent, an electrolyte, and a first initiator to perform a first emulsion polymerization reaction to realize primary grafting, thereby obtaining a first latex; (2) mixing and contacting the first latex, a second graft monomer, a second chain transfer agent, a second emulsifier, and a second initiator to perform a second emulsion polymerization reaction to realize increment grafting, thereby obtaining a second latex; (3) mixing and contacting the second latex and a third initiator to perform a maturation reaction, thereby obtaining a wide particle size distribution rubber graft polymer latex with a core-shell structure.

9. The preparation method according to claim 8, wherein, the rubber emulsion is selected from one or more of a polybutadiene emulsion, a polybutadiene-styrene emulsion, and a polybutyl acrylate emulsion; and / or the solid content of the rubber emulsion is 40-60 wt%, the particle size of the rubber emulsion particles is 100-800 nm, and the polydispersity coefficient is 0.01-0.

05.

10. The production method according to claim 8 or 9, characterized by, In step (1), the amount of the electrolyte added is 0.02-0.25 wt% of the dry basis of the rubber emulsion; and / or The first grafting monomer is 10-100wt% of the dry rubber emulsion.

11. The method of claim 10, wherein, In step (1), The electrolyte is 0.08-0.2wt% of the dry rubber emulsion; and / or The first grafting monomer is 15-30wt% of the dry rubber emulsion.

12. The production method according to claim 8 or 9, characterized by, The electrolyte is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium chloride, and ammonium chloride.

13. The preparation method of claim 8 or 9, wherein, The theoretical solid content of the first latex after step (1) is 35-48wt%; and / or The solid content of the second latex after step (2) is 38-45wt%; and / or The solid content of the wide particle size distribution rubber grafting polymer latex after step (3) is 38-45wt%.

14. The preparation method of claim 13, wherein, The theoretical solid content of the first latex after step (1) is 38-45wt%; and / or The solid content of the second latex after step (2) is 38-42wt%; and / or The solid content of the wide particle size distribution rubber grafting polymer latex after step (3) is 38-43wt%.

15. The preparation method of claim 8 or 9, wherein, The total amount of the first grafting monomer and the second grafting monomer is 50-150wt% of the dry rubber emulsion; and / or The total amount of the first chain transfer agent and the second chain transfer agent is 0.18-1.8wt% of the dry rubber emulsion; the amount of the first chain transfer agent is 30-90wt% of the total amount of the chain transfer agents; and / or The total amount of the first initiator, the second initiator, and the third initiator is 0.16-1.6wt% of the dry rubber emulsion; the amount of the first initiator is 10-40wt% of the total amount of the initiators, the amount of the second initiator is 40-70wt% of the total amount of the initiators, and the amount of the third initiator is 10-40wt% of the total amount of the initiators; and / or The amount of the second emulsifier is 0.16-1.6wt% of the dry rubber emulsion.

16. The preparation method of claim 15, wherein, The total amount of the first grafting monomer and the second grafting monomer is 60-70wt% of the dry rubber emulsion; and / or The total amount of the first chain transfer agent and the second chain transfer agent is 0.4-0.8wt% of the dry rubber emulsion; the amount of the first chain transfer agent is 50-80wt% of the total amount of the chain transfer agents; and / or The total amount of the first initiator, the second initiator, and the third initiator is 0.5-0.8wt% of the dry rubber emulsion; the amount of the first initiator is 14-22wt% of the total amount of the initiators, the amount of the second initiator is 50-70wt% of the total amount of the initiators, and the amount of the third initiator is 20-30wt% of the total amount of the initiators; and / or The amount of the second emulsifier is 0.2-0.5wt% of the dry rubber emulsion.

17. The preparation method of claim 8 or 9, wherein, ​ the first grafting monomer and the second grafting monomer are each independently selected from one or more of acrylonitrile, styrene, alpha-methylstyrene and methyl methacrylate; and / or the first chain transfer agent and the second chain transfer agent are each independently selected from one or more of tert-dodecyl mercaptan and n-dodecyl mercaptan; and / or the first initiator, the second initiator and the third initiator are each independently selected from one or more of tert-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, methylcyclohexane hydroperoxide, p-cymene hydroperoxide cumene and tetrahydronaphthalene hydroperoxide; and / or the second emulsifier is selected from one or more of anionic emulsifiers.

18. The preparation method according to claim 17, wherein, the first grafting monomer and the second grafting monomer are each independently selected from at least two of acrylonitrile, styrene, alpha-methylstyrene and methyl methacrylate, and wherein the content of any one of them is not less than 25-30wt%; and / or the anionic emulsifier is selected from one or more of potassium fatty acid, potassium oleate, potassium disproportionated rosin acid, sodium dodecyl sulfonate and sodium butylnaphthalene sulfonate.

19. The method of claim 18, wherein, the first grafting monomer and the second grafting monomer are each independently selected from a mixture of acrylonitrile, styrene, and wherein the content of any one of them is not less than 25-30wt%.

20. The preparation method according to claim 8 or 9, wherein, the conditions of the first emulsion polymerization reaction include: temperature of 35-60℃, time of 50-70min, and the amount of the washing water is 10-150wt% of the dry basis amount of the rubber emulsion; and / or the conditions of the second emulsion polymerization reaction include: adding electrolyte or not adding electrolyte, temperature of 50-80℃, time of 100-200min, and the amount of the washing water is 35-135wt% of the dry basis amount of the rubber emulsion; and / or the conditions of the aging reaction include: temperature of 60-80℃, time of 15-30min.

21. The production method according to claim 8 or 9, characterized by, The method further comprises: step (1) is carried out in the presence of the first emulsifier, and the amount of the first emulsifier is less than or equal to 1wt% of the dry basis amount of the rubber emulsion; and / or the first emulsifier is selected from one or more of anionic emulsifiers.

22. The method of claim 21, wherein, the anionic emulsifier is selected from one or more of potassium fatty acid, potassium oleate, potassium disproportionated rosin acid, sodium dodecyl sulfonate and sodium butylnaphthalene sulfonate.

23. The wide particle size distribution rubber graft polymer latex with core-shell structure prepared by the preparation method according to any one of claims 8-22.

24. The rubber graft polymer latex having a core-shell structure with a broad particle size distribution according to claim 23, characterized in that, In the wide particle size distribution rubber graft polymer latex, the particle size of the rubber graft polymer is 0.3-1.5μm, and the polydispersity index of the rubber graft polymer is 0.1-0.

5.

25. The rubber graft polymer latex having a core-shell structure with a broad particle size distribution according to claim 24, characterized in that, In the wide particle size distribution rubber graft polymer latex, the particle size of the rubber graft polymer is 0.5-1.2μm; and / or the polydispersity index of the rubber graft polymer is 0.1-0.3; and / or the solid content of the latex is 35-48wt%.

26. A process for the preparation of a rubber graft polymer having a broad particle size distribution with a core-shell structure, characterized in that, The method comprises: i) preparing the wide particle size distribution rubber graft polymer latex with core-shell structure according to the method of any one of claims 8-22; ii) coagulating, washing and drying the wide particle size distribution rubber graft polymer latex having a core-shell structure.

27. The wide particle size distribution rubber graft polymer having a core-shell structure prepared by the preparation method of claim 26, wherein the core structure material of the rubber graft polymer is rubber, and the shell structure material is graft monomer polymer; the particle size of the rubber graft polymer is 0.3-1.5 μm, and the polydispersity coefficient of the rubber graft polymer in the latex is 0.1-0.

5.

28. The wide particle size distribution rubber graft polymer of claim 27, wherein, the particle size of the rubber graft polymer is 0.5-1.2 μm; and / or the polydispersity coefficient of the rubber graft polymer in the rubber graft polymer latex is 0.1-0.3; and / or the "shell / core" mass ratio of the rubber graft polymer is 30-60:

100.

29. The wide particle size distribution rubber graft polymer of claim 28, wherein, the "shell / core" mass ratio of the rubber graft polymer is 40-50:

100.

30. Use of the wide particle size distribution rubber graft polymer having a core-shell structure of any one of claims 1-5, 27-29 in toughening SAN, PP, PVC and PC / ABS resin materials.

31. An ABS resin characterized in that, The ABS resin comprises: the wide particle size distribution rubber graft polymer having a core-shell structure of any one of claims 1-5, 27-29 and SAN resin.

32. The ABS resin of claim 31, wherein, The impact strength of the ABS resin is 20-25 kJ / m 2 , the tensile strength is 40-45 MPa, the tensile elongation at break is 22-35%, the bending strength is 65-71 MPa, and the bending modulus is 2200-2400. and / or the mass ratio of the wide particle size distribution rubber graft polymer to the SAN resin is 0.25-0.35:

1.

33. Use of the ABS resin of claim 31 or 32 in the fields of machinery, electricity, textile, automobile, airplane, and ship.

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