Resin composition as well as preparation method and application thereof

Abstract

The invention provides a resin composition as well as a preparation method and application thereof. The resin composition comprises a combination of alkenyl monomer copolymer resin and a flexibilizer, the flexibilizer has a core-shell structure, the core of the flexibilizer comprises poly-conjugated diene, and the shell of the flexibilizer comprises an alkenyl monomer copolymer; in the resin composition, based on 100% of the cross-sectional area of the core structure of the flexibilizer, the total area of the phase domain without the carbon-carbon double bonds in the core structure is 3%-25%, and the equivalent diameter of the phase domain without the carbon-carbon double bonds is 20-55 nm. Through the design of the alkenyl monomer copolymer resin, the flexibilizer and a phase domain structure in a flexibilizer core structure, the resin composition has high transparency and low haze, meanwhile, the impact strength is high, the toughness is good, and the impact resistance is excellent; the performance requirements on high-transparency and high-impact-resistance materials in the fields of household appliances, automobile parts and the like are fully met.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] ABS resin is usually prepared from three monomers: acrylonitrile (AN), butadiene (BD), and styrene (St). It integrates the hardness and chemical resistance of polyacrylonitrile, the toughness and impact resistance of polybutadiene, and the processability of polystyrene. It is a thermoplastic polymer material with excellent comprehensive properties and is widely used in the fields of electronics, electrical appliances, instruments, automobiles, building materials, etc. Conventional ABS resins are opaque, but with the high-performance requirements of industries such as electronic appliances and automotive parts for materials, the transparency of ABS has become an important development trend in the field of polymer materials.

[0003] Transparent ABS resin is a special grade product among ABS resins. It has excellent transparency, impact resistance, processability, and solvent resistance, and is highly favored in household appliances, automotive parts, communication equipment, and medical equipment. The difference between transparent ABS resin and traditional ABS resin lies in the introduction of the low refractive index monomer methyl methacrylate (MMA), that is, MMA with a low refractive index is copolymerized with St with a high refractive index, and then its refractive index is regulated so that the refractive indices of the matrix phase and the dispersed phase in the transparent ABS resin match each other, and the difference is less than 0.005 to achieve transparency.

[0004] At present, the methods for preparing transparent ABS resin in the industrial field can be divided into two types: bulk polymerization technology and emulsion blending technology. For example, CN106699981A discloses a method for preparing transparent ABS resin using a continuous bulk device. Using butadiene-based rubber as the toughening rubber, at a certain temperature, a certain proportion of chopped toughening rubber, acrylonitrile, styrene, methyl methacrylate, and ethylbenzene are fully stirred in a sol kettle to form a uniform raw rubber solution. The dissolved raw rubber solution is successively sent to four plug flow reactors for bulk polymerization reaction, and finally devolatilization and granulation are carried out to obtain a transparent ABS resin product. CN105008406A discloses a method for preparing transparent ABS resin and a transparent ABS resin composition by emulsion blending technology. Using polybutadiene latex with a size of 250-400 nm as the core layer latex, styrene, acrylonitrile, and methyl methacrylate monomers are graft copolymerized on the surface of the polybutadiene latex by emulsion grafting technology to form particles with a core-shell structure. During the grafting process, a crosslinking agent is introduced to minimize the swelling effect of styrene on butadiene as much as possible, and then the prepared core-shell structure particles are melt-blended with a methyl methacrylate-styrene-acrylonitrile terpolymer (MSAN) resin prepared by the bulk method to obtain a transparent ABS resin.

[0005] Although transparent ABS resins have achieved commercial applications, existing transparent ABS resins are difficult to simultaneously achieve high transparency and excellent impact resistance, which limits their application scenarios. Therefore, developing transparent ABS resins with both high transparency and high impact resistance is an urgent problem to be solved in this field. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition, its preparation method and application. Through the design of vinyl monomer copolymer resin, toughening agent and phase domain structure, the resin composition has high transparency, low haze and excellent impact resistance, fully meeting the performance requirements of high-transparency and high-impact-resistant materials in fields such as household appliances and automotive parts.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted:

[0008] In the first aspect, the present invention provides a resin composition, which includes a combination of a vinyl monomer copolymer resin and a toughening agent; the toughening agent has a core-shell structure, the core of the toughening agent includes a polyconjugated diene, and the shell of the toughening agent includes a vinyl monomer copolymer; in the resin composition, based on the cross-sectional area of the core structure of the toughening agent being 100%, the total area of the phase domains without carbon-carbon double bonds in the core structure is 3%-25%, and the equivalent diameter of the phase domains without carbon-carbon double bonds is 20-55 nm.

[0009] In the resin composition provided by the present invention, the vinyl monomer copolymer resin is used as the continuous phase, and the toughening agent with a core-shell structure is used as the dispersed phase. The shell of the toughening agent includes a vinyl monomer copolymer, which has good compatibility with the continuous phase of the vinyl monomer copolymer resin, enabling the toughening agent to be uniformly dispersed in the continuous phase resin; the core of the toughening agent includes a polyconjugated diene rubber, which has high elasticity and can provide toughness for the resin composition. At the same time, the toughening agent has a specific phase domain structure, and its core structure internally encloses a microstructure composed of non-rubber components, that is, phase domains without carbon-carbon double bonds. Such phase domains with an inclusion structure can make the core structure mainly composed of rubber phase more uniform, can regulate the penetration of light in the corresponding material of the resin composition, and provide higher light transmittance and lower haze for the resin composition; moreover, due to the existence of the inclusion structure inside the core and the distribution of phase domains without carbon-carbon double bonds, the size of the rubber phase in the toughening agent can be larger, which can provide better toughening effect for the resin composition. Therefore, through the design of the vinyl monomer copolymer resin, the toughening agent and the phase domain structure in the core structure of the toughening agent, the resin composition has high transparency and low haze, and at the same time has high impact strength, good toughness and excellent impact resistance.

[0010] In the resin composition, based on the cross-sectional area of the core structure of the toughening agent being 100%, the total area of the phase domains without carbon-carbon double bonds in the core structure is 3%-25%, for example, it can be 4%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22% or 24%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Preferably, it is 5-24%, and more preferably 10-20%.

[0011] The equivalent diameter of the phase domains without carbon-carbon double bonds is 20-55 nm, for example, it can be 22 nm, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, 45 nm, 48 nm, 50 nm, 52 nm or 54 nm, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0012] By making the toughening agent in the resin composition have a specific phase domain structure, the total area of the phase domains without carbon-carbon double bonds is 3%-25%, and its equivalent diameter is 20-55 nm, the present invention can balance the optical properties and toughness of the resin composition, enabling the resin composition to have both high transparency, low haze and excellent impact resistance.

[0013] It should be noted that the microscopic morphologies of the phase domains without carbon-carbon double bonds are the same or different, and each independently is a sphere or an ellipsoid, and its cross-section is circular or elliptical. The "equivalent diameter" is used as a measure of its size.

[0014] Exemplarily, the total area of the phase domains without carbon-carbon double bonds in the core structure is obtained by the following method: The resin composition is processed into a molded body, the molded body is cryo-sectioned and stained, and the cross-section is tested by an electron microscope. The dark-colored part that is stained is the core structure of the toughening agent, and its area is the cross-sectional area of the core structure (counted as 100%). Inside the dark-colored part, there is one or several (≥2) lighter-colored regions, which are the phase domains without carbon-carbon double bonds. The sum of the areas of the lighter-colored regions inside the dark-colored part is the total area of the phase domains without carbon-carbon double bonds in the core structure (3%-25%, which can also be understood as the area ratio of the phase domains without carbon-carbon double bonds in the core structure); the sizes of each lighter-colored region (phase domain without carbon-carbon double bonds) are the same or different, and its equivalent diameter is 20-55 nm.

[0015] It should be noted that both the total area of the phase domains without carbon-carbon double bonds in the core structure of the present invention and the equivalent diameter of the phase domains without carbon-carbon double bonds in the core structure are statistical averages.

[0016] Optionally, the processing method of the molded body includes injection molding.

[0017] Optionally, the thickness of the cryosection is 50-100 nm, for example, it can be 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm or 95 nm, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0018] Optionally, the stain used for staining includes osmium tetroxide, which can stain the part containing non-conjugated double bonds in the cryosection sample; when observed with an electron microscope, it can be seen that the core structure of the toughening agent is stained and has a dark color, and the phase domain inside the core structure contains no carbon-carbon double bonds and is not stained and has a lighter color; the vinyl monomer copolymer resin as the continuous phase also contains no carbon-carbon double bonds and is also light-colored when observed under an electron microscope.

[0019] Optionally, the electron microscope includes a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), and TEM is further preferred.

[0020] Optionally, the magnification of the electron microscope is 30,000-100,000 times, and more preferably 50,000 times.

[0021] Optionally, the area of the dark-colored part to be stained, the area of the region with a lighter color inside the dark-colored part, and the equivalent diameter of the phase domain containing no carbon-carbon double bonds can be statistically calculated by Image J software.

[0022] Exemplarily, the method of statistical calculation includes: calculating and statistically analyzing toughener particles in 10 electron microscope images with a magnification of 50,000 times (each image contains 1-5 analyzable objects) through Image J software to obtain the equivalent diameter of the phase domains in the toughener without carbon-carbon double bonds; the calculation principle of the software is to binarize the electron microscope images to distinguish the phase domains containing carbon-carbon double bonds (white) from the phase domains without carbon-carbon double bonds (black) inside the toughener, only select the toughener particles with clear and definite internal phase domains, and calculate the size of the pixel points in the photo and the equivalent diameter of the phase domains in the toughener without carbon-carbon double bonds according to the scale in the TEM photo. Taking the process of measuring the area and equivalent diameter of one phase domain without carbon-carbon double bonds as an example, the specific method is as follows: Taking a photo with a pixel point size of 1 nm×1 nm as an example for measurement, calculation and statistics. To increase the accuracy of statistics, only the phase domains without carbon-carbon double bonds with an area greater than 100 square nanometers are statistically analyzed. The specific calculation and measurement methods are as follows: First, calculate the centroid of the graph of the phase domain without carbon-carbon double bonds through Image J software (the calculation method of the centroid is tested according to the integral method based on the pixel point coordinates of the shape edge), measure all the diameters passing through the centroid, and take their average value to obtain the average diameter of the phase domain without carbon-carbon double bonds; calculate the area of the phase domain without carbon-carbon double bonds through the pixel point size and the number of points; measure the areas and equivalent diameters of all the phase domains without carbon-carbon double bonds in 10 electron microscope images, and take the average value of the statistical results.

[0023] Preferably, the conjugated diene monomer of the polyconjugated diene includes any one or a combination of at least two of butadiene, isoprene, and chloroprene.

[0024] Preferably, the polymerization monomer of the alkenyl monomer copolymer includes alkenyl monomer A, and the alkenyl monomer A includes a combination of a first acrylate monomer, a first alkenyl aromatic monomer, optionally a first cyano vinyl monomer, and optionally a bifunctional alkenyl monomer.

[0025] Preferably, the mass percentage content of the first acrylate monomer in the alkenyl monomer A is 40%-85%, for example, it can be 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, or 84%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list all the specific point values included in the range.

[0026] Among them, the first acrylate monomer may be an alkyl (meth)acrylate, that is, it includes an alkyl methacrylate and / or an alkyl acrylate; the alkyl group therein is a linear or branched alkyl group with 1 to 20 carbon atoms (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C16, C18, etc.).

[0027] Preferably, the first acrylate monomer includes any one or a combination of at least two of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate.

[0028] Preferably, the first vinyl aromatic monomer includes any one or a combination of at least two of styrene, α-methylstyrene, m-methylstyrene, α-ethylstyrene, p-methylstyrene, and p-tert-butylstyrene.

[0029] Preferably, the mass percentage content of the first vinyl aromatic monomer in the vinyl monomer A is 10% - 50%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, or 48%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0030] Preferably, the first cyano vinyl monomer includes any one or a combination of at least two of acrylonitrile, methacrylonitrile, and ethylacrylonitrile.

[0031] Preferably, the mass percentage content of the first cyano vinyl monomer in the vinyl monomer A is ≤20%, for example, it can be 0, 1%, 2%, 3%, 5%, 8%, 10%, 12%, 15%, or 18%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0032] In the present invention, the difunctional vinyl monomer refers to a monomer containing 2 C═C groups.

[0033] Preferably, the difunctional vinyl monomer includes any one or a combination of at least two of divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dipropylene glycol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, allyl acrylate, and allyl methacrylate.

[0034] Preferably, the mass percentage content of the difunctional vinyl monomer in the vinyl monomer A is ≤ 5%, for example, it can be 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.5% - 2.5%, and more preferably 1% - 2%.

[0035] As a preferred technical solution of the present invention, the core of the toughening agent includes polyconjugated diene, which is obtained by polymerizing conjugated diene monomers and can provide a rubber phase of the core structure, endowing the resin composition with excellent toughness and impact resistance. The shell of the toughening agent is obtained by copolymerizing a first acrylate monomer, a first vinyl aromatic monomer, a first cyano vinyl monomer and a difunctional vinyl monomer, and has good compatibility with the copolymer resin of the vinyl monomer as the continuous phase; on the other hand, during the preparation of the toughening agent, part of the shell chain segments enter the core structure, and by controlling the crosslinking density of the core structure rubber and the introduction of the difunctional vinyl monomer in the shell chain segments, a specific phase domain structure without carbon-carbon double bonds is formed in the core structure, making the core structure more uniform and regulating the light transmittance in the material; at the same time, the phase domain structure without carbon-carbon double bonds is dispersed in the rubber phase, equivalently increasing the rubber content in the toughening agent, enabling the resin composition to better balance high transparency and high impact resistance.

[0036] Preferably, the preparation method of the toughening agent includes:

[0037] (S1) The conjugated diene monomer undergoes an emulsion polymerization reaction in the presence of a first emulsifier, a first initiator and water to obtain an emulsion containing a core polymer;

[0038] (S2) The emulsion containing the core polymer and the vinyl monomer A undergo a polymerization reaction in the presence of a second emulsifier and a second initiator to obtain a core-shell polymer emulsion;

[0039] (S3) The core-shell polymer emulsion is mixed with a coagulant and then undergoes demulsification, solid-liquid separation and drying to obtain the toughening agent.

[0040] Preferably, each of the first emulsifier and the second emulsifier independently includes any one or a combination of at least two of alkyl sulfonates, sulfonated alkyl esters, fatty acid salts, and rosin acid salts.

[0041] Exemplarily, each of the first emulsifier and the second emulsifier independently includes any one or a combination of at least two of dodecylbenzenesulfonate, dodecyl sulfate, dodecyl sulfonate, octanoate, decanoate, laurate, myristate, palmitate, stearate, oleate, linoleate. The first emulsifier and the second emulsifier may also be complex mixed emulsifiers such as beef tallow fatty acid salt or rosin acid salt.

[0042] Preferably, the "salt" involved in the first emulsifier and the second emulsifier includes alkali metal salts (such as potassium salt, sodium salt, lithium salt, etc.) and / or ammonium salts.

[0043] Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first emulsifier is 1 - 5 parts, for example, it can be 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts or 4.8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0044] Preferably, the first initiator includes any one or a combination of at least two of persulfates, peroxides, redox initiators.

[0045] As a preferred technical solution of the present invention, the first initiator is a water-soluble initiator, and further preferably a persulfate, such as any one or a combination of at least two of sodium persulfate, potassium persulfate, ammonium persulfate.

[0046] Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first initiator is 0.01 - 1 part, for example, it can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0047] Preferably, the materials for the emulsion polymerization reaction further include an electrolyte and a first molecular weight controller.

[0048] Preferably, the electrolyte includes inorganic salts, and further preferably any one or a combination of at least two of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO3, K4P2O7, K3PO4, Na3PO4, K2HPO4, Na2HPO4.

[0049] Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the electrolyte is 0.1 - 5 parts, for example, it can be 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts or 4.8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0050] Preferably, the first molecular weight regulator includes a thiol compound, and more preferably any one or a combination of at least two of n - octyl mercaptan, tert - dodecyl mercaptan, n - dodecyl mercaptan, n - tetradecyl mercaptan, and n - octadecyl mercaptan.

[0051] Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first molecular weight regulator is 0.1 - 1 part, for example, it can be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0052] Preferably, the mass ratio of the conjugated diene monomer to water in step (S1) is 1:(0.5 - 2), for example, it can be 1:0.6, 1:0.8, 1:1, 1:1.1, 1:1.2, 1:1.4, 1:1.5, 1:1.6 or 1:1.8, etc.

[0053] Preferably, the temperature of the emulsion polymerization reaction in step (S1) is 55 - 90 °C, for example, it can be 58 °C, 60 °C, 62 °C, 65 °C, 68 °C, 70 °C, 72 °C, 75 °C, 78 °C, 80 °C, 82 °C, 85 °C or 88 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0054] Preferably, the time of the emulsion polymerization reaction in step (S1) is 10 - 40 h, for example, it can be 12 h, 15 h, 16 h, 18 h, 20 h, 22 h, 24 h, 25 h, 26 h, 28 h, 30 h, 32 h, 34 h, 35 h, 36 h or 38 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0055] Preferably, the emulsion polymerization reaction in step (S1) includes a first - stage polymerization and a second - stage polymerization carried out in sequence.

[0056] Preferably, the temperature of the first-stage polymerization is 55-75°C, for example, it can be 58°C, 60°C, 62°C, 65°C, 68°C, 70°C, 72°C or 74°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0057] Preferably, the time of the first-stage polymerization is 6-24 h, for example, it can be 8 h, 10 h, 12 h, 14 h, 15 h, 16 h, 18 h, 20 h or 24 h, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0058] Preferably, the temperature of the second-stage polymerization is 65-85°C, for example, it can be 66°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C or 84°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0059] Preferably, the time of the second-stage polymerization is 4-16 h, for example, it can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h or 15 h, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0060] Preferably, the method of the emulsion polymerization reaction in step (S1) includes: adding 50%-90% (such as 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 478%, 80%, 82%, 85% or 88%, etc.) of the conjugated diene monomer, the first emulsifier, the first initiator, the electrolyte, the first molecular weight regulator and water in the reaction device according to the formula amount, reacting at 55-75°C for 6-24 h, and then adding the remaining conjugated diene monomer according to the formula amount, and reacting at 65-85°C for 4-16 h to obtain an emulsion containing the core polymer.

[0061] Preferably, the particle size of the core polymer in the emulsion in step (S1) is 50-400 nm, for example, it can be 80 nm, 100 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 350 nm or 380 nm, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0062] Preferably, the gel content of the core polymer is 45%-75%, for example, it can be 46%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70% or 73%, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 50%-74%, and more preferably 55%-73%.

[0063] Exemplarily, the particle size of the core polymer in the emulsion of the core polymer is obtained by testing with a laser diffraction particle size analyzer; preferably, the laser diffraction particle size analyzer uses Mastersizer 3000+ and is tested according to the method in Standard GB / T 19077-2016, and the data is the average particle size (D 50 ).

[0064] An exemplary sample dilution method is as follows: Take 30 μL of the core polymer emulsion and add it to 500 mL of pure water. Gently stir to disperse the core polymer emulsion in water under the condition of ensuring no bubbles are generated, and it can be used for testing.

[0065] Exemplarily, the gel content of the core polymer is obtained by testing according to the method in Standard SH / T 1050-2014 "Determination of Gel Content of Synthetic Raw Rubber".

[0066] Preferably, the mass ratio of the core polymer to the vinyl monomer A is (0.1-5):1, for example, it can be 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1 or 4.8:1, etc.

[0067] It should be noted that the emulsion containing the core polymer obtained in step (S1) undergoes a polymerization reaction with the vinyl monomer A, and the mass ratio of the core polymer to the vinyl monomer A is calculated based on the mass of the core polymer itself (i.e., the solid content of the emulsion), excluding solvents (such as water) therein.

[0068] Preferably, based on the total mass of the core polymer and the vinyl monomer A being 100 parts, the mass of the second emulsifier is 0.1-2 parts, for example, it can be 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts or 1.8 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0069] Preferably, the second initiator is a fat-soluble initiator, including any one or a combination of at least two of organic peroxides, azo compounds, and redox initiators.

[0070] Preferably, the organic peroxide includes any one or a combination of at least two of cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and benzoyl peroxide.

[0071] Preferably, the azo compound includes azobisisobutyronitrile and / or azodiisooctanenitrile.

[0072] Preferably, the oxidant in the redox initiator includes an organic peroxide, such as any one or a combination of at least two of cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and benzoyl peroxide; the reductant in the redox initiator includes any one or a combination of at least two of sodium formaldehyde sulfoxylate, ferrous sulfate, sodium pyrrolidone, sodium sulfite, sodium pyrophosphate, and glucose.

[0073] Preferably, based on the total mass of the core polymer and vinyl monomer A being 100 parts, the mass of the second initiator is 0.01 - 1 part, for example, it can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0074] Preferably, the materials for the polymerization reaction in step (S2) further include a second molecular weight controller.

[0075] Preferably, the second molecular weight controller includes thiol compounds, and more preferably any one or a combination of at least two of n-octyl mercaptan, tert-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan.

[0076] Preferably, based on the total mass of the core polymer and vinyl monomer A being 100 parts, the mass of the second molecular weight controller is 0.1 - 1 part, for example, it can be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0077] Preferably, the temperature of the polymerization reaction in step (S2) is 50-85°C, for example, it can be 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C or 84°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0078] Preferably, the time of the polymerization reaction in step (S2) is 4-12 h, for example, it can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or 11 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0079] Preferably, the particle size of the core-shell polymer in the core-shell polymer emulsion is 80-500 nm, for example, it can be 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 320 nm, 350 nm, 380 nm, 400 nm, 420 nm, 450 nm or 480 nm, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0080] Exemplarily, the particle size of the core-shell polymer in the core-shell polymer emulsion is obtained by testing with a laser diffraction particle size analyzer. Preferably, the laser diffraction particle size analyzer adopts Mastersizer 3000+, and the test is carried out according to the method in Standard GB / T 19077-2016, and the data is the average particle size (D 50 ).

[0081] An exemplary sample dilution method is as follows: Take 30 μL of the core-shell polymer emulsion and add it to 500 mL of pure water. Gently stir to disperse the core-shell polymer emulsion in water under the condition of ensuring no bubbles are generated, and it can be used for testing.

[0082] Preferably, the coagulant includes an acid and / or a water-soluble salt, and more preferably any one or a combination of at least two of sulfuric acid, hydrochloric acid, phosphoric acid, calcium chloride, magnesium chloride, barium chloride, and magnesium sulfate.

[0083] Preferably, based on 100 parts by mass of the solid content of the core-shell polymer emulsion, the mass of the coagulant is 0.1-20 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 15 parts or 18 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0084] Preferably, the demulsification is carried out under stirring conditions.

[0085] Preferably, the temperature of the demulsification is 60 - 95 °C. For example, it can be 62 °C, 65 °C, 68 °C, 70 °C, 72 °C, 75 °C, 78 °C, 80 °C, 82 °C, 85 °C, 88 °C, 90 °C, 92 °C or 94 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0086] Preferably, the time of the demulsification is 0.1 - 3 h. For example, it can be 0.2 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.2 h, 2.5 h or 2.8 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0087] Preferably, the method of solid - liquid separation includes: centrifuging the product obtained from demulsification, discarding the supernatant, and collecting the solid.

[0088] Preferably, the weight - average molecular weight of the acetone - soluble matter in the toughening agent is 70000 - 150000 g / mol. For example, it can be 80000 g / mol, 90000 g / mol, 100000 g / mol, 110000 g / mol, 120000 g / mol, 130000 g / mol or 140000 g / mol, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0089] Exemplarily, the weight - average molecular weight of the acetone - soluble matter in the toughening agent is obtained by the following method: Add 0.5 g of the toughening agent (powder) into a high - speed centrifuge tube, add 10 mL of acetone and shake and disperse at 30 °C for 4 h. Then, centrifuge at a speed of 30000 revolutions to dissolve the part soluble in acetone in the upper clear acetone, and the insoluble part precipitates at the bottom of the centrifuge tube. Remove the acetone in the upper clear liquid to obtain the part soluble in acetone (i.e., the acetone - soluble matter). It is generally considered that the chain length of the polymer soluble in acetone (the acetone - soluble matter) is equivalent to the molecular weight of the shell layer in the core - shell structured toughening agent, and it is generally represented by the weight - average molecular weight. The test method for the weight - average molecular weight can refer to GB / T 27843 - 2011. The preferred mobile phase is tetrahydrofuran, the preferred equipment is ACQUITY advanced polymer chromatography (APC) system, the preferred selected chromatographic column is a series connection of one Styragel HR4 and one Styragel HR3, the test temperature is generally 40 - 50 °C, and the flow rate is 1 mL / min.

[0090] Preferably, the polymerization monomers of the alkenyl monomer copolymer resin include an alkenyl monomer B, and the alkenyl monomer B includes a combination of a second acrylate monomer, a second vinyl aromatic monomer, and optionally a second cyano vinyl monomer.

[0091] Preferably, the mass percentage content of the second acrylate monomer in the alkenyl monomer B is 40%-85%, for example, it can be 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82% or 84%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0092] Among them, the second acrylate monomer can be an alkyl (meth)acrylate, that is, it includes an alkyl methacrylate and / or an alkyl acrylate; the alkyl therein is a linear or branched alkyl of C1-C20 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C16, C18, etc.).

[0093] Preferably, the second acrylate monomer includes any one or a combination of at least two of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate.

[0094] Preferably, the mass percentage content of the second vinyl aromatic monomer in the alkenyl monomer B is 10%-50%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45% or 48%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0095] Preferably, the second vinyl aromatic monomer includes any one or a combination of at least two of styrene, α-methylstyrene, m-methylstyrene, α-ethylstyrene, p-methylstyrene, and p-tert-butylstyrene.

[0096] Preferably, the mass percentage content of the second cyano vinyl monomer in the alkenyl monomer B is ≤15%, for example, it can be 0, 1%, 2%, 3%, 5%, 8%, 10%, 12% or 14%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0097] Preferably, the second cyano vinyl monomer includes any one or a combination of at least two of acrylonitrile, methacrylonitrile, and ethylacrylonitrile.

[0098] Preferably, the weight average molecular weight of the vinyl monomer copolymer resin is 70,000 - 150,000 g / mol. For example, it can be 80,000 g / mol, 90,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, or 140,000 g / mol, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0099] Exemplarily, the weight average molecular weight of the vinyl monomer copolymer resin is obtained by testing according to the method of GB / T 27843 - 2011. Specifically, the mobile phase used is preferably tetrahydrofuran, the selected equipment is preferably an ACQUITY Advanced Polymer Chromatography (APC) system, the selected chromatographic column is preferably a series connection of one Styragel HR4 and one Styragel HR3, the test temperature is generally 40 - 50 °C, and the flow rate is 1 mL / min.

[0100] As a preferred technical solution of the present invention, the preparation method of the vinyl monomer copolymer resin includes: polymerizing the vinyl monomer B to obtain the vinyl monomer copolymer resin.

[0101] Preferably, the third initiator includes any one or a combination of at least two of organic peroxides, azo compounds, and redox initiators. Further preferably, it is any one or a combination of at least two of cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, and azobisisobutyronitrile.

[0102] Preferably, the polymerization reaction is carried out in the presence of a third initiator.

[0103] Preferably, based on 100 parts by mass of the vinyl monomer B, the mass of the third initiator is ≤1 part. For example, it can be 0, 0.01 part, 0.02 part, 0.05 part, 0.08 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0104] Preferably, the polymerization reaction is carried out in the presence of a third molecular weight controller.

[0105] Preferably, the third molecular weight regulator comprises a thiol compound, more preferably any one or a combination of at least two of n-octyl mercaptan, tert-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan.

[0106] Preferably, based on 100 parts by mass of the alkenyl monomer B, the mass of the third molecular weight regulator is 0.01 - 1 part, for example, it can be 0.02 part, 0.05 part, 0.08 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, or 0.9 part, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the specific point values included in this range are not exhaustively listed in the present invention.

[0107] Preferably, the polymerization reaction is carried out in the presence of an organic solvent.

[0108] Preferably, the organic solvent includes aromatic solvents, more preferably any one or a combination of at least two of toluene, ethylbenzene, diphenylmethane, 1,2-diphenylethane, and anisole.

[0109] Preferably, the mass ratio of the alkenyl monomer B to the organic solvent is 1:(0.1 - 1), for example, it can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, or 1:0.9, etc., more preferably 1:(0.15 - 0.5).

[0110] Preferably, the temperature of the polymerization reaction is 100 - 250 °C, for example, it can be 110 °C, 120 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, or 240 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the specific point values included in this range are not exhaustively listed in the present invention, more preferably 130 - 230 °C.

[0111] Preferably, the time of the polymerization reaction is 0.5 - 4 h, for example, it can be 0.8 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, or 4 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the specific point values included in this range are not exhaustively listed in the present invention.

[0112] Preferably, after the polymerization reaction is completed, it further includes the steps of devolatilization and pelletization.

[0113] Preferably, the devolatilization is carried out by an evaporator to remove the organic solvent and unreacted monomers.

[0114] Preferably, the pelletization is carried out by a transfer pump and an extruder.

[0115] Preferably, the processing temperature for granulation is 200 - 250°C, for example, it can be 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C or 245°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0116] Preferably, the resin composition comprises the following in parts by mass:

[0117] Alkenyl monomer copolymer resin 68 - 92 parts

[0118] Toughening agent 8 - 32 parts;

[0119] Specifically, the mass parts of the alkenyl monomer copolymer resin are 68 - 92 parts, for example, it can be 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 84 parts, 85 parts, 86 parts, 88 parts or 90 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 70 - 90 parts.

[0120] The mass parts of the toughening agent are 8 - 32 parts, for example, it can be 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts or 30 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 10 - 30 parts.

[0121] Preferably, the absolute value of the difference in refractive index between the alkenyl monomer copolymer resin and the toughening agent ≤ 0.004, for example, it can be 0, 0.0001, 0.0003, 0.0005, 0.0008, 0.001, 0.0012, 0.0015, 0.0018, 0.002, 0.0022, 0.0025, 0.0028, 0.003, 0.0032, 0.0035 or 0.0038, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, ≤ 0.0032.

[0122] It should be noted that whether the refractive index of the alkenyl monomer copolymer resin ≥ the refractive index of the toughening agent, or the refractive index of the alkenyl monomer copolymer resin < the refractive index of the toughening agent, is within the scope of the present invention, as long as the absolute value of the difference in their refractive indices ≤ 0.004, preferably ≤ 0.0032, more preferably ≤ 0.002, the transparency of the resin composition can be further improved.

[0123] Preferably, the refractive index of the vinyl monomer copolymer resin is 1.480 - 1.550. For example, it can be 1.485, 1.490, 1.495, 1.500, 1.505, 1.510, 1.515, 1.520, 1.525, 1.530, 1.535, 1.540 or 1.545, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 1.500 - 1.535, and more preferably 1.510 - 1.520.

[0124] Preferably, the refractive index of the toughening agent is 1.480 - 1.550. For example, it can be 1.485, 1.490, 1.495, 1.500, 1.505, 1.510, 1.515, 1.520, 1.525, 1.530, 1.535, 1.540 or 1.545, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 1.500 - 1.535, and more preferably 1.510 - 1.520.

[0125] Exemplarily, the refractive indices of the vinyl monomer copolymer resin and the toughening agent can be measured by the method in the standard GB / T 39691 - 2020 "Determination of Refractive Index of Plastics".

[0126] In the present invention, the vinyl monomer copolymer resin serves as the continuous phase in the resin composition and can provide excellent strength, hardness, scratch resistance, weather resistance and transparency. Preferably, the mass percentage content of the vinyl monomer copolymer resin in the resin composition is 68% - 92%. For example, it can be 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88% or 90%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 70% - 90%.

[0127] The toughening agent serves as the dispersed phase in the resin composition and has a specific phase domain structure. On the one hand, it can improve toughness and impact resistance, and on the other hand, when compounded with the continuous phase, it endows the resin composition with high transparency and low haze. Preferably, the mass percentage content of the toughening agent in the resin composition is 8% - 32%. For example, it can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28% or 30%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. Further preferably, it is 10% - 30%.

[0128] It should be noted that the resin composition of the present invention may further include any other additives that are motivated to be added in the art.

[0129] Preferably, the resin composition further includes 0.05 - 0.4 parts by mass of an antioxidant. For example, the mass parts of the antioxidant can be 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.15 parts, 0.18 parts, 0.2 parts, 0.22 parts, 0.25 parts, 0.28 parts, 0.3 parts, 0.32 parts, 0.35 parts or 0.38 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0130] Preferably, the antioxidant includes any one or a combination of at least two of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, and thioester antioxidants.

[0131] Preferably, the antioxidant includes a combination of a primary antioxidant and a secondary antioxidant.

[0132] Preferably, the primary antioxidant includes any one or a combination of at least two of 2,6 - di - tert - butyl - p - cresol (BHT), 2,2'-methylenebis(4 - ethyl - 6 - tert - butylphenol), 2,2'-methylenebis(4 - methyl - 6 - tert - butylphenol), 2,2'-methylenebis(4 - methyl - 6 - cyclohexylphenol), 2,2'-methylenebis(4 - methyl - 6 - nonylphenol), octadecyl 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl)propionate, 1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl)butane, and pentaerythritol tetrakis(3,5 - di - tert - butyl - 4 - hydroxyhydrocinnamate).

[0133] Preferably, the secondary antioxidant includes tris(nonylphenyl) phosphite and / or dilauryl thiodipropionate.

[0134] Preferably, the resin composition further includes 0.05 - 0.3 parts by mass of a lubricant. The mass parts of the lubricant can be 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.15 parts, 0.18 parts, 0.2 parts, 0.22 parts, 0.25 parts or 0.28 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0135] Preferably, the lubricant includes any one or a combination of at least two of silicone oil, silicone powder, paraffin wax, stearic acid, magnesium stearate, butyl stearate, erucamide, oleamide, and ethylene bisstearamide.

[0136] Second aspect, the present invention provides a preparation method of the resin composition as described in the first aspect, the preparation method comprising: melt-blending an alkenyl monomer copolymer resin and a toughening agent and then extruding to obtain the resin composition.

[0137] Preferably, the materials for melt-blending further include an antioxidant and / or a lubricant.

[0138] Preferably, the melt-blending is carried out in a screw extruder.

[0139] Preferably, the screw extruder is a twin-screw extruder.

[0140] Preferably, the temperature of the screw extruder is 180 - 250 °C, for example, it can be 185 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C or 240 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0141] Preferably, after the extrusion, it further includes the steps of pelletizing and drying.

[0142] Third aspect, the present invention provides an application of the resin composition as described in the first aspect in household appliances, automotive parts, communication equipment or medical equipment.

[0143] Compared with the prior art, the present invention has the following beneficial effects:

[0144] In the resin composition provided by the present invention, the alkenyl monomer copolymer resin is used as the continuous phase, and the toughening agent with a core-shell structure is used as the dispersed phase. The toughening agent has a specific phase domain structure. Through the design of the alkenyl monomer copolymer resin, the toughening agent and the phase domain structure in the core structure of the toughening agent, the resin composition has high transparency and low haze, and at the same time has high impact strength, good toughness and excellent impact resistance performance, fully meeting the performance requirements for high-transparency and high-impact-resistant materials in the fields of household appliances, automotive parts, etc. Description of the Drawings

[0145] Figure 1 It is a transmission electron microscope image of the resin composition provided in Example 1;

[0146] Figure 2 It is Figure 1 The binary image of the transmission electron microscope image. Detailed Embodiments

[0147] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0148] As used herein, the terms "comprising", "including", "having", "containing" or any other variation thereof are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article or apparatus that comprises the recited elements is not necessarily limited to those elements, but may also include other elements not expressly listed or elements inherent to such composition, step, method, article or apparatus.

[0149] In the present invention, features defined as "first", "second", "third" may explicitly or implicitly include one or more of such features, which are used to distinguish and describe features, without order or importance. In the description of the present invention, unless otherwise specified, the meaning of "a plurality of" is two or more.

[0150] In the following specific embodiments of the present invention, the test methods for material properties are as follows:

[0151] (1) The equivalent diameter and area of the phase domains without carbon-carbon double bonds

[0152] The resin composition to be tested is injection-molded into a part according to the method of GB / T 17037.1-1997 "Preparation of Injection Molded Specimens of Thermoplastic Materials - Part 1: General Principles and Preparation of Multipurpose and Long Strip Specimens". The surface part of the injection-molded part is cut off, and a sample with a thickness of 70 nm is prepared using a cryo-ultramicrotome. Then it is stained with osmium tetroxide. Referring to JY / T0581-2020 "General Rules for Transmission Electron Microscopy Analysis Methods", a transmission electron microscope (TEM, model JEOL JEM-1230) is used to test and observe the phase structure. The dark stained part is the core structure of the toughening agent, and the inside of the dark part contains a lighter part, which is the phase domain without carbon-carbon double bonds; 10 electron microscope photos with a magnification of 50,000 times are selected (each picture contains at least 1 analyzable object, and the images near the edge of the picture will not be included in the calculation). The transmission electron microscope images are processed and calculated using ImageJ software. When the software calculates, the electron microscope photos are first binarized to distinguish the part without carbon-carbon double bonds (white) from the phase domain containing carbon-carbon double bonds (black), and then according to the size of the scale bar in the TEM photo, the size of the pixel points in the photo is calculated to calculate the binarized image. The specific method is as follows: Taking a picture with a pixel point size of 1 nm×1 nm as an example for measurement, calculation and statistics. To increase the accuracy of statistics, only the phase domains without carbon-carbon double bonds with an area greater than 100 square nanometers are statistically analyzed: First, the centroid of the graph of the phase domain without carbon-carbon double bonds is calculated using Image J software (the calculation method of the centroid is tested according to the pixel coordinates of the shape edge by the integral method), all diameters passing through the centroid are measured, and their average value is taken to obtain the average diameter of the phase domain without carbon-carbon double bonds; the area of the phase domain without carbon-carbon double bonds is calculated through the pixel point size and the number; the areas and equivalent diameters of all the phase domains without carbon-carbon double bonds in 10 TEM images are measured, and the results are averaged.

[0153] (2) Transparency and haze

[0154] The resin composition to be tested is injection-molded into a square plate with dimensions of 50 mm×50 mm×2 mm and tested according to the method in the standard GB / T2410-2008 "Standard Test Method for Transmittance and Haze of Transparent Plastics".

[0155] (3) Impact resistance

[0156] It is tested according to the standard GB / T 1843-2008 "Plastics - Determination of Izod Impact Strength", notch type A.

[0157] (4) Gel content

[0158] It is tested according to the method in the standard SH / T 1050-2014 "Determination of Gel Content of Synthetic Rubber".

[0159] (5) The particle size of the core polymer in the emulsion of the core polymer and the particle size of the core-shell polymer in the core-shell polymer emulsion are obtained by testing with a laser diffraction particle size analyzer (model Mastersizer 3000+), and the testing method refers to GB / T 19077-2016 "Laser Diffraction Method for Particle Size Distribution".

[0160] (6) Refractive index

[0161] The toughener or vinyl monomer copolymer resin is pressed into a 2-mm-thick smooth sheet on both sides at 220 °C by a flat vulcanizer and tested with an Abbe refractometer (model ATAGO DR-M2), and the testing method refers to GB / T 39691-2020 "Determination of Refractive Index of Plastics".

[0162] (7) Weight-average molecular weight

[0163] The test is carried out according to the method in GB / T 27843-2011, specifically including: using an ACQUITY Advanced Polymer Chromatography (APC) system, with a chromatographic column consisting of a Styragel HR4 and a Styragel HR3 in series, the mobile phase being tetrahydrofuran, the test temperature being 45 °C, and the flow rate being 1 mL / min.

[0164] (8) Weight-average molecular weight of acetone-soluble matter in the toughener

[0165] Add 0.5 g of the toughener to be tested (powder) into a high-speed centrifuge tube, add 10 mL of acetone and shake and disperse at 30 °C for 4 h, then dissolve the part soluble in acetone in the upper acetone supernatant by a centrifuge at a rotation speed of 30,000 revolutions; take the upper supernatant, remove the acetone therein, and the acetone-soluble matter can be obtained, and its weight-average molecular weight is tested by the method in (7).

[0166] In the following specific embodiments of the present invention, the reagents whose preparation methods are not specified are all commercially available chemicals.

[0167] Preparation of tougheners A1-A12

[0168] Preparation Example 1

[0169] Toughener A1, which has a core-shell structure, is prepared as follows:

[0170] (1) By mass, 70 parts of butadiene, 3 parts of disproportionated rosin potassium, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.5 parts of tert-dodecyl mercaptan and 100 parts of deionized water were added to a stainless-steel pressure-resistant reactor, and the temperature was raised to 60 °C under stirring conditions for 20 h to complete the first-stage reaction; then 30 parts of butadiene were added and reacted at 70 °C for 8 h to complete the second-stage reaction; the temperature was naturally cooled to room temperature to obtain an emulsion containing a core polymer. The average particle size of the core polymer in the emulsion was 310 nm, and the gel content of the core polymer was 65%;

[0171] (2) By mass, 65 parts of the emulsion obtained in step (1) (calculated based on the core polymer, that is, 65 parts based on the solid content mass of the emulsion), 35 parts of comonomer (19 parts of methyl methacrylate, 10.5 parts of styrene, 5 parts of acrylonitrile, 0.5 parts of ethylene glycol dimethacrylate), 0.6 parts of potassium tallowate, and 1 part of tert-dodecyl mercaptan were stirred and mixed for 2 h, and then 0.8 parts of a redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) were added. The temperature was raised to 75 °C under stirring conditions for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer was 352 nm;

[0172] (3) By mass, 50 parts of the core-shell polymer emulsion obtained in step (2) (solid content of 40.2%), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) were mixed, and the temperature was raised to 80 °C and stirred for 1 h to demulsify, and then centrifuged for dehydration and dried to obtain toughening agent A1, whose weight-average molecular weight of acetone-soluble matter was 71200 g / mol and refractive index was 1.5183.

[0173] Preparation Example 2

[0174] Toughening agent A2, which has a core-shell structure, and its preparation method is as follows:

[0175] (1) By mass, 70 parts of butadiene, 3 parts of disproportionated rosin potassium, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.5 parts of tert-dodecyl mercaptan and 100 parts of deionized water were added to a stainless-steel pressure-resistant reactor, and the temperature was raised to 60 °C under stirring conditions for 20 h to complete the first-stage reaction; then 30 parts of butadiene were added and reacted at 70 °C for 8 h to complete the second-stage reaction; the temperature was naturally cooled to room temperature to obtain an emulsion containing a core polymer. The average particle size of the core polymer in the emulsion was 310 nm, and the gel content of the core polymer was 65%;

[0176] (2) By mass, 73 parts of the emulsion obtained in step (1) (calculated based on the core polymer), 0.6 part of potassium butyro-fatty acid, 1 part of tert-dodecyl mercaptan, 0.8 part of a redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) were continuously added with 27 parts of comonomers (13.5 parts of methyl methacrylate, 8 parts of styrene, 5 parts of acrylonitrile, 0.5 part of ethylene dimethacrylate) under stirring conditions. After stirring and mixing for 3 h, the temperature was raised to 75 °C and reacted for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer was 361 nm;

[0177] (3) By mass, 50 parts of the core-shell polymer emulsion obtained in step (2) (with a solid content of 40.3%), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) were mixed, and the temperature was raised to 80 °C and stirred for 1 h to demulsify. Then, it was centrifuged for dehydration and dried to obtain toughening agent A1, whose weight-average molecular weight of acetone-soluble matter was 124000 g / mol and refractive index was 1.5175.

[0178] Preparation Example 3

[0179] Toughening agent A3, which has a core-shell structure, is prepared as follows:

[0180] (1) By mass, 70 parts of isoprene, 3 parts of potassium disproportionated rosin, 0.8 part of potassium persulfate, 2 parts of sodium carbonate, 0.5 part of tert-dodecyl mercaptan, and 100 parts of deionized water were added to a stainless steel pressure-resistant reactor. The temperature was raised to 55 °C under stirring conditions and reacted for 20 h to complete the first-stage reaction. Then, 30 parts of butadiene were added and reacted at 70 °C for 8 h to complete the second-stage reaction. It was naturally cooled to room temperature to obtain an emulsion containing a core polymer. The average particle size of the core polymer in the emulsion was 315 nm, and the gel content of the core polymer was 57%;

[0181] (2) By mass, 65 parts of the emulsion obtained in step (1) (calculated based on the core polymer), 35 parts of comonomers (15 parts of ethyl methacrylate, 14.5 parts of styrene, 5 parts of acrylonitrile, 0.5 part of ethylene dimethacrylate), 0.6 part of potassium butyro-fatty acid, and 1 part of tert-dodecyl mercaptan were stirred and mixed for 2 h, and then 0.8 part of a redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) was added. The temperature was raised to 75 °C under stirring conditions and reacted for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer was 355 nm;

[0182] (3) Mix 50 parts (solid content: 41.2%) of the core-shell polymer emulsion obtained in step (2), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) by mass, heat up to 80 °C, and carry out demulsification under stirring for 1 h, then carry out centrifugal dehydration and drying to obtain toughening agent A3, whose weight-average molecular weight of acetone-soluble matter is 112,000 g / mol and refractive index is 1.5173.

[0183] Preparation Example 4

[0184] Toughening agent A4, which has a core-shell structure, and its preparation method is as follows:

[0185] (1) Add 70 parts of butadiene, 3 parts of potassium disproportionated rosin, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.5 parts of tert-dodecyl mercaptan, and 100 parts of deionized water into a stainless-steel pressure-resistant reactor, heat up to 55 °C under stirring conditions and react for 20 h to complete the first-stage reaction; then add 30 parts of chloroprene and react at 65 °C for 8 h to complete the second-stage reaction; naturally cool down to room temperature to obtain an emulsion containing a core polymer, the average particle size of the core polymer in the emulsion is 303 nm, and the gel content of the core polymer is 70%;

[0186] (2) Mix 65 parts (based on the core polymer) of the emulsion obtained in step (1), 35 parts of comonomers (14 parts of methyl methacrylate, 15.5 parts of α-methylstyrene, 5 parts of acrylonitrile, 0.5 parts of ethylene glycol dimethacrylate), 0.6 parts of potassium tallowate, and 1 part of tert-dodecyl mercaptan, stir and mix for 1 h, then add 0.8 parts of a redox initiator system (prepared according to the mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8), heat up to 75 °C under stirring conditions and react for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer is 350 nm;

[0187] (3) Mix 50 parts (solid content: 40.5%) of the core-shell polymer emulsion obtained in step (2), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) by mass, heat up to 80 °C, and carry out demulsification under stirring for 1 h, then carry out centrifugal dehydration and drying to obtain toughening agent A4, whose weight-average molecular weight of acetone-soluble matter is 97,000 g / mol and refractive index is 1.5151.

[0188] Preparation Example 5

[0189] Toughening agent A5, which has a core-shell structure, and its preparation method is as follows:

[0190] (1) By mass, 70 parts of isoprene, 3 parts of potassium disproportionated rosin, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.5 parts of tert-dodecyl mercaptan and 100 parts of deionized water are added into a stainless steel pressure-resistant reactor, and the temperature is raised to 55 °C under stirring conditions for 15 h to complete the first-stage reaction; then 30 parts of chloroprene are added, and the reaction is carried out at 75 °C for 14 h to complete the second-stage reaction; the temperature is naturally cooled to room temperature to obtain an emulsion containing core polymer, wherein the average particle size of the core polymer is 278 nm and the gel content of the core polymer is 72%;

[0191] (2) By mass, 65 parts of the emulsion obtained in step (1) (calculated as the core polymer), 35 parts of comonomers (15 parts of methyl methacrylate, 15 parts of styrene, 4.5 parts of methacrylonitrile, 0.5 parts of ethylene glycol dimethacrylate), 0.6 parts of potassium tallowate, 1 part of tert-dodecyl mercaptan are stirred and mixed for 0.5 h, and then 0.8 parts of a redox initiation system (prepared with the mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate being 1:0.02:0.6:0.8) are added. The temperature is raised to 75 °C under stirring conditions for 10 h to obtain a core-shell polymer emulsion, wherein the particle size of the core-shell polymer is 310 nm;

[0192] (3) By mass, 50 parts of the core-shell polymer emulsion obtained in step (2) (with a solid content of 41.6%), 40 parts of deionized water and 2 parts of a coagulant (magnesium sulfate) are mixed, and the temperature is raised to 80 °C and stirred for 1 h to demulsify, and then centrifuged for dehydration and dried to obtain toughening agent A5, the weight-average molecular weight of its acetone-soluble matter is 83000 g / mol, and the refractive index is 1.5143.

[0193] Preparation Example 6

[0194] Toughening agent A6, which has a core-shell structure, is prepared as follows:

[0195] (1) By mass, 70 parts of butadiene, 3 parts of potassium disproportionated rosin, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.2 parts of tert-dodecyl mercaptan and 100 parts of deionized water are added into a stainless steel pressure-resistant reactor, and the temperature is raised to 60 °C under stirring conditions for 20 h to complete the first-stage reaction; then 30 parts of butadiene and 0.2 parts of potassium persulfate are added, and the reaction is carried out at 80 °C for 15 h to complete the second-stage reaction; the temperature is naturally cooled to room temperature to obtain an emulsion containing core polymer, wherein the average particle size of the core polymer is 300 nm and the gel content of the core polymer is 78%;

[0196] (2) By mass, 65 parts of the emulsion obtained in step (1) (based on the core polymer), 35 parts of comonomers (19 parts of methyl methacrylate, 10.5 parts of styrene, 5 parts of acrylonitrile, 0.5 part of ethylene glycol dimethacrylate), 0.6 part of potassium tallowate, and 1 part of tert-dodecyl mercaptan were stirred and mixed for 2 h, and then 0.8 part of a redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) was added. The temperature was raised to 75 °C under stirring and reacted for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer was 352 nm;

[0197] (3) By mass, 50 parts of the core-shell polymer emulsion obtained in step (2) (with a solid content of 40.5%), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) were mixed, and the temperature was raised to 80 °C and stirred for 1 h for demulsification. Then, it was centrifuged for dehydration and dried to obtain toughening agent A6, whose weight-average molecular weight of acetone-soluble matter was 84,500 g / mol and refractive index was 1.5183.

[0198] Preparation Example 7

[0199] Toughening agent A7, which has a core-shell structure, is prepared as follows:

[0200] (1) By mass, 70 parts of isoprene, 3 parts of potassium disproportionated rosin, 0.8 part of potassium persulfate, 2 parts of sodium carbonate, 3.5 parts of tert-dodecyl mercaptan, and 100 parts of deionized water were added to a stainless-steel pressure-resistant reactor. The temperature was raised to 55 °C under stirring and reacted for 20 h to complete the first-stage reaction. Then, 30 parts of butadiene were added and reacted at 60 °C for 8 h to complete the second-stage reaction. It was naturally cooled to room temperature to obtain an emulsion containing a core polymer, where the average particle size of the core polymer was 305 nm and the gel content of the core polymer was 43%;

[0201] (2) By mass, 65 parts of the emulsion obtained in step (1) (based on the core polymer), 35 parts of comonomers (15 parts of ethyl methacrylate, 14.5 parts of styrene, 5 parts of acrylonitrile, 0.5 part of ethylene glycol dimethacrylate), 0.6 part of potassium tallowate, and 1 part of tert-dodecyl mercaptan were stirred and mixed for 2 h, and then 0.8 part of a redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) was added. The temperature was raised to 75 °C under stirring and reacted for 10 h to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer was 386 nm;

[0202] (3) Mix 50 parts (solid content: 41.3%) of the core-shell polymer emulsion obtained in step (2), 40 parts of deionized water, and 2 parts of a coagulant (magnesium sulfate) by mass, heat up to 80 °C, and carry out demulsification with stirring for 1 h. Then, carry out centrifugal dehydration and drying to obtain toughening agent A7. The weight-average molecular weight of the acetone-soluble matter thereof is 83,400 g / mol, and the refractive index is 1.5192.

[0203] Preparation Example 8

[0204] Toughening agent A8, the difference from Preparation Example 1 is only that the difunctional monomer in step (2) is replaced with methyl methacrylate of the same mass, and other materials, dosages, and process parameters are the same as those in Preparation Example 1. The particle size of the core-shell polymer in the obtained core-shell polymer emulsion is 335 nm. The weight-average molecular weight of the acetone-soluble matter of toughening agent A8 is 67,100 g / mol, and the refractive index is 1.5183.

[0205] Preparation Example 9

[0206] Toughening agent A9, the difference from Preparation Example 1 is only that the dosage of ethylene glycol dimethacrylate in step (2) is 2.5 parts, and the dosage of methyl methacrylate is 17 parts, and other materials, dosages, and process parameters are the same as those in Preparation Example 1. The particle size of the core-shell polymer in the obtained core-shell polymer emulsion is 365 nm. The weight-average molecular weight of the acetone-soluble matter of toughening agent A9 is 92,300 g / mol, and the refractive index is 1.5183.

[0207] Preparation Example 10

[0208] Toughening agent A10, the difference from Preparation Example 1 is only that the comonomer in step (2) is 35 parts, including 23 parts of styrene, 11.5 parts of acrylonitrile, and 0.5 part of ethylene glycol dimethacrylate, and other materials, dosages, and process parameters are the same as those in Preparation Example 1. The particle size of the core-shell polymer in the obtained core-shell polymer emulsion is 355 nm. The weight-average molecular weight of the acetone-soluble matter of toughening agent A10 is 76,000 g / mol, and the refractive index is 1.5323.

[0209] Preparation Example 11

[0210] Toughening agent A11, which is different from Preparation Example 1 only in step (1). The specific method is as follows: By mass, 70 parts of butadiene, 1.7 parts of divinylbenzene, 3 parts of disproportionated rosin potassium, 0.8 parts of potassium persulfate, 2 parts of sodium carbonate, 0.5 parts of tert-dodecyl mercaptan and 100 parts of deionized water are added to a stainless steel pressure-resistant reactor. Under stirring conditions, the temperature is raised to 60 °C and reacted for 20 h to complete the first-stage reaction; then 30 parts of butadiene are added and reacted at 70 °C for 8 h to complete the second-stage reaction; it is naturally cooled to room temperature to obtain an emulsion containing core polymer. The average particle size of the core polymer in the emulsion is 305 nm, and the gel content of the core polymer is 87.5%.

[0211] Using the above emulsion, a core-shell polymer emulsion is prepared by the same method as in step (2) of Preparation Example 1, where the particle size of the core-shell polymer is 325 nm; then, by the same method as in step (3) of Preparation Example 1, toughening agent A11 is prepared. The weight-average molecular weight of the acetone-soluble matter is 112000 g / mol, and its refractive index is 1.5192.

[0212] Preparation Example 12

[0213] Toughening agent A12, which is different from Preparation Example 1 only in step (2). The specific method is as follows: Under stirring conditions, the temperature is raised to 75 °C. By mass, the following mixture is continuously added to 65 parts of the emulsion obtained in step (1) (65 parts based on the core polymer, that is, 65 parts based on the solid content mass of the emulsion) for 10 hours, including: 35 parts of comonomer (19 parts of methyl methacrylate, 10.5 parts of styrene, 5 parts of acrylonitrile, 0.5 parts of ethylene glycol dimethacrylate), 0.6 parts of potassium tallowate, 1 part of tert-dodecyl mercaptan and 0.8 parts of redox initiator system (prepared with a mass ratio of cumene hydroperoxide, ferrous sulfate, glucose, and sodium pyrophosphate of 1:0.02:0.6:0.8) to obtain a core-shell polymer emulsion, where the particle size of the core-shell polymer is 342 nm; then, by the same method as in step (3) of Preparation Example 1, toughening agent A12 is prepared. The weight-average molecular weight of the acetone-soluble matter is 70320 g / mol, and the refractive index is 1.5183.

[0214] Preparation of vinyl monomer copolymer resins B1 - B6

[0215] Preparation Example 13

[0216] Vinyl monomer copolymer resin B1 is obtained by copolymerizing methyl methacrylate, styrene, and acrylonitrile. The specific method includes:

[0217] Weigh the following raw materials by parts by mass: 68.4 parts of methyl methacrylate, 26.6 parts of styrene, 5 parts of acrylonitrile, 30 parts of toluene, 0.15 part of tert-dodecyl mercaptan, and 0.2 part of benzoyl peroxide; keep the reaction temperature in the reactor at 155 °C, and continuously add the aforementioned raw materials into the reactor, so that the average reaction time is 2 h, and discharge the polymerization solution; after heating the polymerization solution discharged from the reactor in a preheater and evaporating the unreacted monomers and solvents in an evaporator, keep the temperature at 210 °C, transfer the polymer melt with a transfer pump, and process the resin into pellets with an extruder to obtain the vinyl monomer copolymer resin B1, whose weight-average molecular weight is 82000 g / mol and refractive index is 1.5179.

[0218] Preparation Example 14

[0219] Vinyl monomer copolymer resin B2, which is different from Preparation Example 13 only in the comonomers, specifically as follows: 62.4 parts of methyl methacrylate, 22.6 parts of styrene, 15 parts of acrylonitrile; other materials, dosages, and process parameters are the same as those in Preparation Example 13, to obtain the vinyl monomer copolymer resin B2, whose weight-average molecular weight is 73000 g / mol and refractive index is 1.5164.

[0220] Preparation Example 15

[0221] Vinyl monomer copolymer resin B3, which is different from Preparation Example 13 only in the comonomers, specifically as follows: 57 parts of ethyl methacrylate, 35 parts of styrene, 8 parts of acrylonitrile; other materials, dosages, and process parameters are the same as those in Preparation Example 13, to obtain the vinyl monomer copolymer resin B3, whose weight-average molecular weight is 101000 g / mol and refractive index is 1.5151.

[0222] Preparation Example 16

[0223] Vinyl monomer copolymer resin B4, which is different from Preparation Example 13 only in the comonomers, specifically as follows: 70 parts of methyl methacrylate, 22 parts of α-methylstyrene, 8 parts of acrylonitrile; other materials, dosages, and process parameters are the same as those in Preparation Example 13, to obtain the vinyl monomer copolymer resin B4, whose weight-average molecular weight is 135000 g / mol and refractive index is 1.5184.

[0224] Preparation Example 17

[0225] Vinyl monomer copolymer resin B5, which is different from Preparation Example 13 only in the comonomers, specifically as follows: 65 parts of methyl methacrylate, 25 parts of styrene, 10 parts of methacrylonitrile; other materials, dosages, and process parameters are the same as those in Preparation Example 13, to obtain the vinyl monomer copolymer resin B5, whose weight-average molecular weight is 122000 g / mol and refractive index is 1.5180.

[0226] Production Example 18

[0227] The vinyl monomer copolymer resin B6, which is different from Production Example 13 only in that the comonomers are different. Specifically, it contains 23.5 parts of styrene and 76.5 parts of acrylonitrile. Other materials, dosages, and process parameters are the same as those in Production Example 13, obtaining the vinyl monomer copolymer resin B6 with a weight average molecular weight of 85,000 g / mol and a refractive index of 1.5328.

[0228] The following are several exemplary embodiments of the resin composition provided by the present invention. In the following embodiments, the specific information of the materials used is as follows:

[0229] (1) Toughening agent

[0230] A1 - A12, from Production Examples 1 - 12.

[0231] (2) Vinyl monomer copolymer resin

[0232] B1 - B6, from Production Examples 13 - 18.

[0233] (3) Antioxidant

[0234] Primary antioxidant: Pentaerythritol tetrakis(3,5 - di - tert - butyl - 4 - hydroxyhydrocinnamate), commercially available;

[0235] Secondary antioxidant: Dilauryl thiodipropionate, commercially available.

[0236] (4) Lubricant

[0237] Ethylene bisstearamide, commercially available.

[0238] Examples 1 - 11, Comparative Examples 1 - 8

[0239] A resin composition, the types and dosages of each component are shown in Table 1 and Table 2, and the dosage unit of each component is "parts" (by mass).

[0240] The preparation method of the resin composition includes: placing each component in a mixer according to the formula amount, mixing at a speed of 150 rpm for 5 minutes to obtain a premix; adding the premix into a twin - screw extruder for melt blending, then extruding, pelletizing, drying, and cooling to obtain the resin composition; wherein, the temperature of the twin - screw extruder is 230 °C and the screw speed is 130 rpm.

[0241] Table 1

[0242]

[0243]

[0244]

[0245] Table 2

[0246]

[0247]

[0248] Comparative Example 9

[0249] Commercially available transparent ABS resin (Terlux HD 2802, purchased from Ineos) was tested by the same method as in Example 1. The total area of the phase domains without double bonds was 0 (i.e., the phase domains without carbon-carbon double bonds were not detected), and the impact strength was 5 kJ / m 2 , the transparency was 89%, and the haze was 3.5%.

[0250] The transmission electron micrograph of the resin composition provided in Example 1 is as shown in Figure 1 shown, and after its binarization is as shown in Figure 2 shown, where the dark circular (elliptical) regions are the core structures of the toughening agent, and there are several lighter-colored parts inside the dark regions, which are the phase domains without carbon-carbon double bonds. Their average diameter is 50 nm, and the proportion of the total area in the cross-section of the core structure is 13%; the phase domain data of other examples and comparative examples are shown in Table 1. According to Table 1 and Table 2, it can be seen that the present invention designs the toughening agent to form a specific phase domain structure, so that in the resin compositions of Examples 1-11, the phase domains without carbon-carbon double bonds have a size of 23-54 nm, and their area proportion in the core structure is 7%-23%, making the transparency of the resin composition ≥90%, the haze ≤4.5%, and the impact strength ≥15 kJ / m 2 , taking into account high transparency and excellent impact resistance. At the same time, according to the performance data of Example 1 and Examples 6-9, using different vinyl monomer copolymer resins in combination with the toughening agent to make the phase domain structure meet the limitations of the present invention can endow the resin composition with high transparency, low haze, and excellent impact performance.

[0251] According to Comparative Examples 1-8, if the phase domain structure without carbon-carbon double bonds in the resin composition is not within the scope defined by the present invention, the reduction of the internal phase domain size and the decrease of the content will lead to a significant increase in the haze of the material and a decrease in the impact performance; the increase of the internal phase domain size and the increase of the content will lead to a significant decrease in the impact performance of the material. Comparative Example 9 is a commercially available transparent ABS resin. Although its transparency is already better than that of traditional ABS resins, the size and total area of its internal phase domains without carbon-carbon double bonds do not meet the limitations of the present invention, resulting in its significantly lower impact strength than that of the present invention and also having certain deficiencies in transparency.

[0252] The applicant declares that the present invention illustrates the resin composition, its preparation method and application through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises a combination of a vinyl monomer copolymer resin and a toughening agent; the toughening agent has a core-shell structure, the core of the toughening agent comprises a polyconjugated diene, and the shell of the toughening agent comprises a vinyl monomer copolymer; In the resin composition, based on the cross-sectional area of the core structure of the toughening agent being 100%, the total area of the phase domains without carbon-carbon double bonds in the core structure is 3%-25%, and the equivalent diameter of the phase domains without carbon-carbon double bonds is 20-55 nm.

2. The resin composition according to claim 1, wherein The conjugated diene monomer of the polyconjugated diene comprises any one or a combination of at least two of butadiene, isoprene, and chloroprene.

3. The resin composition according to claim 1 or 2, characterized in that, The polymerization monomer of the vinyl monomer copolymer comprises a vinyl monomer A, and the vinyl monomer A comprises a combination of a first acrylate monomer, a first vinyl aromatic monomer, optionally a first cyano vinyl monomer, and optionally a bifunctional vinyl monomer; Preferably, the mass percentage content of the first acrylate monomer in the vinyl monomer A is 40%-85%; Preferably, the first acrylate monomer comprises any one or a combination of at least two of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate; Preferably, the first vinyl aromatic monomer comprises any one or a combination of at least two of styrene, α-methylstyrene, m-methylstyrene, α-ethylstyrene, p-methylstyrene, and p-tert-butylstyrene; Preferably, the mass percentage content of the first vinyl aromatic monomer in the vinyl monomer A is 10%-50%; Preferably, the first cyano vinyl monomer comprises any one or a combination of at least two of acrylonitrile, methacrylonitrile, and ethylacrylonitrile; Preferably, the mass percentage content of the first cyano vinyl monomer in the vinyl monomer A is ≤20%; Preferably, the bifunctional vinyl monomer comprises any one or a combination of at least two of divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dipropylene glycol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, allyl acrylate, and allyl methacrylate; Preferably, the mass percentage content of the bifunctional vinyl monomer in the vinyl monomer A is ≤5%.

4. The resin composition according to claim 3, wherein The preparation method of the toughening agent comprises: (S1) A conjugated diene monomer undergoes an emulsion polymerization reaction in the presence of a first emulsifier, a first initiator, and water to obtain an emulsion containing a core polymer; (S2) The emulsion containing the core polymer and the vinyl monomer A undergo a polymerization reaction in the presence of a second emulsifier and a second initiator to obtain a core-shell polymer emulsion; (S3) The core-shell polymer emulsion is mixed with a coagulant and then undergoes demulsification, solid-liquid separation, and drying to obtain the toughening agent.

5. The resin composition according to claim 4, wherein The first emulsifier and the second emulsifier each independently comprise any one or a combination of at least two of alkyl sulfonates, sulfonated alkyl esters, fatty acid salts, and rosin acid salts; Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first emulsifier is 1-5 parts; Preferably, the first initiator includes any one or a combination of at least two of persulfates, peroxides, and redox initiators, and more preferably persulfates; Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first initiator is 0.01 - 1 part; Preferably, the materials for the emulsion polymerization reaction further include an electrolyte and a first molecular weight regulator; Preferably, the electrolyte includes inorganic salts, and more preferably any one or a combination of at least two of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO3, K4P2O7, K3PO4, Na3PO4, K2HPO4, Na2HPO4; Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the electrolyte is 0.1 - 5 parts; Preferably, the first molecular weight regulator includes thiol compounds, and more preferably any one or a combination of at least two of n-octyl mercaptan, tert-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan; Preferably, based on 100 parts by mass of the conjugated diene monomer, the mass of the first molecular weight regulator is 0.1 - 1 part; Preferably, the mass ratio of the conjugated diene monomer to water in step (S1) is 1:(0.5 - 2); Preferably, the temperature of the emulsion polymerization reaction in step (S1) is 55 - 90 °C, and the time is 10 - 40 h; Preferably, the emulsion polymerization reaction in step (S1) includes a first-stage polymerization and a second-stage polymerization carried out in sequence; Preferably, the temperature of the first-stage polymerization is 55 - 75 °C, and the time is 6 - 24 h; Preferably, the temperature of the second-stage polymerization is 65 - 85 °C, and the time is 4 - 16 h; Preferably, the method of the emulsion polymerization reaction in step (S1) includes: adding 50% - 90% of the formulated amount of the conjugated diene monomer, the first emulsifier, the first initiator, the electrolyte, the first molecular weight regulator, and water to the reaction device, reacting at 55 - 75 °C for 6 - 24 h, then adding the remaining formulated amount of the conjugated diene monomer, and reacting at 65 - 85 °C for 4 - 16 h to obtain an emulsion containing the core polymer; Preferably, the particle size of the core polymer in the emulsion in step (S1) is 50 - 400 nm; Preferably, the gel content of the core polymer is 45% - 75%; Preferably, the mass ratio of the core polymer to the vinyl monomer A is (0.1 - 5):1; Preferably, based on 100 parts by mass of the total mass of the core polymer and the vinyl monomer A, the mass of the second emulsifier is 0.1 - 2 parts; Preferably, the second initiator includes any one or a combination of at least two of organic peroxides, azo compounds, and redox initiators; Preferably, based on 100 parts by mass of the total mass of the core polymer and the vinyl monomer A, the mass of the second initiator is 0.01 - 1 part; Preferably, the materials for the polymerization reaction in step (S2) further include a second molecular weight regulator; Preferably, the second molecular weight regulator includes a thiol compound, and more preferably any one or at least two combinations of n-octyl mercaptan, tert-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan; Preferably, based on the total mass of the core polymer and vinyl monomer A being 100 parts, the mass of the second molecular weight regulator is 0.1 - 1 part; Preferably, the temperature of the polymerization reaction in step (S2) is 50 - 85 °C, and the time is 4 - 12 h; Preferably, the particle size of the core-shell polymer in the core-shell polymer emulsion is 80 - 500 nm; Preferably, the coagulant includes an acid and / or a water-soluble salt, and more preferably any one or at least two combinations of sulfuric acid, hydrochloric acid, phosphoric acid, calcium chloride, magnesium chloride, barium chloride, and magnesium sulfate; Preferably, based on the solid content mass of the core-shell polymer emulsion being 100 parts, the mass of the coagulant is 0.1 - 20 parts; Preferably, the temperature of demulsification is 60 - 95 °C, and the time is 0.1 - 3 h; Preferably, the weight average molecular weight of the acetone-soluble matter in the toughening agent is 70000 - 150000 g / mol.

6. The resin composition according to claim 1, characterized in that, The polymerization monomers of the vinyl monomer copolymer resin include vinyl monomer B, and vinyl monomer B includes a combination of a second acrylate monomer, a second vinyl aromatic monomer, and optionally a second cyano vinyl monomer; Preferably, the mass percentage content of the second acrylate monomer in vinyl monomer B is 40% - 85%; Preferably, the second acrylate monomer includes any one or at least two combinations of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate; Preferably, the mass percentage content of the second vinyl aromatic monomer in vinyl monomer B is 10% - 50%; Preferably, the second vinyl aromatic monomer includes any one or at least two combinations of styrene, α-methylstyrene, m-methylstyrene, α-ethylstyrene, p-methylstyrene, and p-tert-butylstyrene; Preferably, the mass percentage content of the second cyano vinyl monomer in vinyl monomer B is ≤15%; Preferably, the second cyano vinyl monomer includes any one or at least two combinations of acrylonitrile, methacrylonitrile, and ethylacrylonitrile; Preferably, the weight average molecular weight of the vinyl monomer copolymer resin is 70000 - 150000 g / mol.

7. The resin composition according to claim 1, characterized in that, The resin composition includes the following in parts by mass: Vinyl monomer copolymer resin 68 - 92 parts Toughening agent 8 - 32 parts; Preferably, the absolute value of the difference in refractive index between the vinyl monomer copolymer resin and the toughening agent is ≤0.

004.

8. The resin composition according to claim 7, wherein The resin composition further includes 0.05 - 0.4 part of an antioxidant in parts by mass; Preferably, the resin composition further includes 0.05 - 0.3 part of a lubricant in parts by mass.

9. A method for preparing a resin composition according to any one of claims 1-7, characterized in that, The preparation method includes: melt-blending and extruding the vinyl monomer copolymer resin and the toughening agent to obtain the resin composition.

10. Use of a resin composition according to any one of claims 1-7 in household appliances, automotive parts, communication equipment or medical equipment.

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