ABS (Acrylonitrile Butadiene Styrene) resin composition as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) resin composition as well as a preparation method and application thereof. The ABS resin composition comprises a graft copolymer, SAN resin and a functional group substituted tetrahydronaphthalene compound, wherein the functional group comprises one or more of an ester group, a carbonyl group, tertiary carbon, quaternary carbon, unsaturated carbon, secondary amine or tertiary amine. The content of the tetrahydronaphthalene compound substituted by the functional group in the ABS resin composition is 200 to 3200 ppm. The ABS resin composition has excellent mechanical properties.

Description

Technical Field

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

[0002] The homopolymerization and copolymerization of styrene are classical in free radical polymerization, with a unique self-initiation mechanism, involving the homopolymerization or copolymerization of various resins, such as polystyrene resin (PS), poly(α-methylstyrene) resin (PαMS), acrylonitrile-butadiene-styrene resin (ABS), acrylonitrile-styrene-acrylate resin (ASA), acrylonitrile-styrene resin (SAN), methyl methacrylate-butadiene-styrene resin (MBS), methyl methacrylate-styrene resin (MS), and other resins.

[0003] Styrene-based rubber can be prepared by using peroxide or azo initiators in an aqueous solution of an emulsifier. According to the Smith-Ewart kinetic model, the reaction rate is relatively high in the constant-rate polymerization stage (Interval Ⅱ), but as it enters the decelerating polymerization stage (Interval Ⅲ), the monomer droplets disappear and the monomer concentration in the aqueous phase decreases, and the reaction rate also gradually decreases. In the prior art, the conversion rate is increased by adding initiators at the end of the reaction. However, excessive addition of the above initiators not only has limited improvement in the conversion rate, but also has a negative impact on the mechanical properties of the material due to a higher degree of crosslinking or a lower molecular weight. Another type of styrene-based resin can also be prepared by bulk polymerization and solution polymerization. Similar to the above situation, increasing the amount of initiator added in this system can increase the conversion rate to a certain extent, but it will also cause a decrease in the molecular weight of the resin material and have a negative impact on the impact performance of the material. Summary of the Invention

[0004] The object of the present invention is to overcome the above defects or deficiencies, and to provide an ABS resin composition, which includes a tetrahydronaphthalene compound substituted with a functional group, and the functional group includes one or more of an ester group, a carbonyl group, a tertiary carbon, a quaternary carbon, an unsaturated carbon, a secondary amine, or a tertiary amine. The mechanical properties of the ABS resin composition are better.

[0005] To achieve the above object, the present invention is realized by the following technical solutions:

[0006] An ABS resin composition, which includes a graft copolymer and a SAN resin, and the content of the tetrahydronaphthalene substituted with the functional group shown in Formula I in the ABS resin composition is 200 to 3200 ppm;

[0007]

[0008] Among them, at least one of A to H is a functional substituent, and the functional substituent includes one or more of an ester group, a carbonyl group, a tertiary carbon, a quaternary carbon, an unsaturated carbon, a secondary amine or a tertiary amine;

[0009] Preferably, the tertiary carbon includes -CH((CH2) x R)((CH2) y R); the quaternary carbon includes -C((CH2) x R)((CH2) y R)((CH2) z R); the unsaturated carbon includes -(CH2) x CN, =CH(CH2) x R, =C((CH2) x R))((CH2) y R); the secondary amine includes -NH(CH2) x R; the tertiary amine includes -N((CH2) x R))((CH2) y R); the ester group includes -COO(CH2) x R; the carbonyl group includes -CO(CH2) x R;

[0010] x, y, and z in the functional substituent are each independently selected from any integer value from 0 to 15; preferably selected from any integer value from 0 to 3;

[0011] Each R is independently selected from hydrogen, methyl, amino, cyano, phenyl, hydroxyl, -COOR2, -COR2, carboxyl or aldehyde; R2 is a straight-chain or branched-chain alkane with 0 to 18 carbon atoms, preferably R2 is a straight-chain or branched-chain alkane with 0 to 3 or 10 to 14 carbon atoms.

[0012] It should be noted that the content of the functional group-substituted tetrahydronaphthalene shown in Formula I in the ABS resin composition is 200 to 3200 ppm, such as but not limited to 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm, 2000 ppm, 2100 ppm, 2200 ppm, 2300 ppm, 2400 ppm, 2500 ppm, 2600 ppm, 2700 ppm, 2800 ppm, 2900 ppm, 3000 ppm, 3100 ppm or 3200 ppm, etc., or the range between any of the above values.

[0013] Furthermore, the ABS resin composition comprises the following components calculated by weight:

[0014] Graft copolymer: 15 - 45 parts;

[0015] SAN resin: 55 - 85 parts;

[0016] Other components: 0 - 2 parts;

[0017] The content of the functional group-substituted tetrahydronaphthalene shown in Formula I in the graft copolymer is 250 - 3200 ppm; and the content of the functional group-substituted tetrahydronaphthalene shown in Formula I in the SAN resin is 200 - 2000 ppm.

[0018] Specifically, the content of the functional group-substituted tetrahydronaphthalene shown in Formula I in the graft copolymer is 250 to 3200 ppm, such as but not limited to 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm, 2000 ppm, 2100 ppm, 2200 ppm, 2300 ppm, 2400 ppm, 2500 ppm, 2600 ppm, 2700 ppm, 2800 ppm, 2900 ppm, 3000 ppm, 3100 ppm or 3200 ppm, etc., or the range between any of the above values.

[0019] Specifically, the content of the functional group-substituted tetrahydronaphthalene shown in Formula I in the SAN resin is 200 to 2000 ppm, such as but not limited to 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm or 2000 ppm, or the range between any of the above values.

[0020] Further, A to D are each independently selected from -CH((CH2) x R)((CH2) y R), -(CH2) x CN, -C((CH2) x R)((CH2) y R)((CH2) z R), =CH(CH2) x R, =C((CH2) x R))((CH2) y R), -NH(CH2) x R, -N((CH2) x R))((CH2) y R), -CO(CH2) x R or -COO(CH2) xR; and / or

[0021] E to H are each independently selected from -CH((CH2) x R)((CH2) y R)、-C((CH2) x R)((CH2) y R)((CH2) z R)、-NH(CH2) x R, -N((CH2) x R))((CH2) y R)、-CO(CH2) x R or -COO(CH2) x R;

[0022] Further, A to D are each independently selected from one or more of cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, =C(CN)2, -CH2CN, -COOCH3, -NHCOCH3 or -COOCH2CH3; or

[0023] E to H are each independently selected from one or more of cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, -CH2CN, -COOCH3, -NHCOCH3 or -COOCH2CH3.

[0024] Furthermore, A to H also include non-functional substituents, and the non-functional substituents include one or more of hydroxyl, carboxyl, phenyl or amino.

[0025] Furthermore, the functional group-substituted tetralin is:

[0026]

[0027]

[0028] One or more of .

[0029] The graft copolymer is a graft copolymer of a conjugated diene polymer; further, the graft copolymer is a core-shell structure polymer with a conjugated diene polymer as a core and a copolymer including an aromatic vinyl monomer and an alkenyl nitrile monomer as a shell.

[0030] Further, the graft copolymer comprises 100 parts by weight of polyconjugated diene units and 30 to 80 parts by weight of graft monomer units;

[0031] The polyconjugated diene comprises:

[0032] (a): 50 to 100% by weight of monomer A1, where monomer A1 is selected from at least one of butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, isoprene or piperylene;

[0033] Further, monomer A1 is butadiene and / or isoprene.

[0034] (b): 0 to 10% by weight of at least one polyfunctional crosslinking monomer A2; the functionality of polyfunctional crosslinking monomer A2 is greater than or equal to 2;

[0035] Further, polyfunctional crosslinking monomer A2 can be at least one of allyl methacrylate, allyl acrylate, divinylbenzene, diethylene glycol dimethacrylate, 3-(triallylsilyl)propyl acrylate, N-methylolacrylamide, diacetone acrylamide, divinyltetramethoxydisilane or 1,4-bis(vinyldimethylsilyl)benzene.

[0036] Even further, polyfunctional crosslinking monomer A2 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate or divinyltetramethoxydisilane.

[0037] (c): 0 to 50% by weight of other monomer A3, where monomer A3 is selected from at least one of styrene, α-methylstyrene, C2-C4 alkylstyrene, acrylonitrile, methacrylonitrile, chloroprene, C1-C8 alkyl (meth)acrylate, alkylene glycol di(meth)acrylate and vinyl methyl ether;

[0038] Further, monomer A3 is at least one of styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate or methyl methacrylate.

[0039] The graft monomer comprises:

[0040] (d): 50 to 100% by weight of aryl vinyl monomer B1, where aryl vinyl monomer B1 is selected from styrene, α-methylstyrene or a mixture of styrene and at least one of α-methylstyrene, p-methylstyrene and C1-C8 alkyl (meth)acrylate; preferably, 60 to 90% by weight of aryl vinyl monomer B1;

[0041] Further, aryl vinyl monomer B1 is at least one of styrene, methyl acrylate or methyl methacrylate.

[0042] (e): 0 to 50% by weight of monomer B2, said monomer B2 being selected from acrylonitrile or a mixture of acrylonitrile and at least one selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids; preferably, 10 to 40% by weight of monomer B2.

[0043] Furthermore, said monomer B2 is acrylonitrile and / or acrylamide.

[0044] The polyconjugated diene unit is obtained by polymerizing the above monomers A1, A2, A3, and said polymerization includes emulsion polymerization. The polyconjugated diene usually exists in the form of a latex, and optional polyconjugated diene latexes include polybutadiene latex, poly(2,3-dimethyl-1,3-butadiene), 2-ethyl-1,3-butadiene latex, polyisoprene or polymethylpentadiene latex.

[0045] Furthermore, said polyconjugated diene latex is polybutadiene latex and / or polybutadiene-styrene latex.

[0046] Specifically, the gel content of said polyconjugated diene latex is 40 to 95 wt%, preferably 65 to 80 wt%.

[0047] Specifically, the average particle size of said polyconjugated diene latex is 60 to 600 nm.

[0048] The solid content of said polyconjugated diene latex is 35 to 60 wt%.

[0049] The polyconjugated diene latex of the present invention can be obtained by purchasing commercially or by self-preparation, and no special limitation is imposed on its source.

[0050] In some specific embodiments, based on 100 parts by weight of the solid content of the polyconjugated diene, the graft copolymer further includes 0.1 to 2 parts by weight of an initiator, 0.2 to 4 parts by weight of an activator, 0.1 to 1 part by weight of a molecular weight regulator, and 0.25 to 2.5 parts by weight of an emulsifier.

[0051] The solid content of the polyconjugated diene is the non-volatile content of the polyconjugated diene latex.

[0052] The initiator in the present invention includes one or more of redox initiators, azo initiators or peroxide initiators.

[0053] Specifically, said redox initiator is one or more of cumene hydroperoxide, 1-(4-isopropylphenyl)-1-methyl hydroperoxide, 1-(4-tolyl)-1-methyl hydroperoxide or tert-butyl hydroperoxide.

[0054] The azo initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyr amidine hydrochloride, or azobisisobutimidazoline hydrochloride.

[0055] The peroxide initiator is one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl benzoyl peroxide, or methyl ethyl ketone peroxide.

[0056] Specifically, the redox initiator and the activator are used in combination.

[0057] The activator in the present invention includes an aqueous solution of ferrous sulfate, a complexing agent, and a reducing sugar.

[0058] In some specific embodiments, the complexing agent includes one or more of aminocarboxylates, hydroxycarboxylates, organic phosphonates, or phosphates.

[0059] The reducing sugar includes one or more of glucose, lactose, fructose, galactose, or maltose.

[0060] The molecular weight regulator in the present invention includes one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, tetradecyl mercaptan, tridecyl mercaptan, undecyl mercaptan, or decyl mercaptan.

[0061] The emulsifier in the present invention includes one or more of saturated or unsaturated fatty acids with C8-C 20 potassium or sodium salts of disproportionated rosin, dodecylbenzenesulfonic acid, or dodecylsulfonic acid.

[0062] The present invention also provides a method for preparing a graft copolymer. The graft copolymer can be prepared by emulsion polymerization. The preparation method includes the following steps:

[0063] Mix the raw materials evenly and carry out a staged temperature-raising reaction, followed by coagulation, dehydration, and drying to obtain the graft copolymer; the raw materials include a polyconjugated diene, a graft monomer, an initiator, an activator, a molecular weight regulator, and an emulsifier.

[0064] Specifically, for the staged temperature-raising reaction, the temperature of the first-stage reaction is 50-75°C, and the reaction time is 10-60 min; the temperature of the second-stage reaction is 55-80°C, and the reaction time is 60-240 min; the temperature of the third-stage reaction is 60-90°C, and the reaction time is 50-150 min.

[0065] The present invention also discloses a SAN resin. The SAN resin is a copolymer including an aromatic vinyl monomer and an alkenyl nitrile monomer.

[0066] Furthermore, the SAN resin includes the following monomer units:

[0067] (a): At least one vinyl aromatic monomer B1 in an amount of 65 to 90% by weight, where the vinyl aromatic monomer B1 is selected from styrene, α-methylstyrene, or a mixture of styrene and at least one selected from α-methylstyrene, p-methylstyrene, and C1-C8 alkyl (meth)acrylates; preferably, at least one vinyl aromatic monomer B1 in an amount of 70 to 80 parts by weight;

[0068] Further, the vinyl aromatic monomer B1 is at least one of styrene, methyl acrylate, or methyl methacrylate.

[0069] (b): At least one monomer B2 in an amount of 10 to 35% by weight, where the monomer B2 is selected from acrylonitrile, methacrylonitrile, acrylamide, or a mixture of acrylonitrile and at least one other monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids, and imides of unsaturated carboxylic acids; preferably, at least one monomer B2 in an amount of 20 to 30 parts by weight;

[0070] Further, the monomer B2 is acrylonitrile and / or acrylamide.

[0071] (c): At least one polyfunctional crosslinking monomer B3 in an amount of 0 to 10% by weight; the functionality of the polyfunctional crosslinking monomer B3 is greater than or equal to 2.

[0072] Specifically, the polyfunctional crosslinking monomer B3 is selected from at least one of allyl methacrylate, allyl acrylate, divinylbenzene, diethylene glycol dimethacrylate, 3-(triallylsilyl)propyl acrylate, N-methylolacrylamide, diacetoneacrylamide, divinyltetramethoxydisilane, or 1,4-bis(vinyldimethylsilyl)benzene.

[0073] Further, the polyfunctional crosslinking monomer B3 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate, or divinyltetramethoxydisilane.

[0074] The SAN resin is obtained by copolymerizing the above monomers B1, B2, and B3, and the copolymerization includes random copolymerization, alternating copolymerization, syndiotactic copolymerization, or block copolymerization.

[0075] Further, the copolymerization is completed by emulsion polymerization. In some specific embodiments, the SAN resin further includes 0 to 0.5% by weight of an initiator and 0.01 to 0.5% by weight of a molecular weight regulator.

[0076] Other initiators in the present invention include azo initiators or peroxide initiators.

[0077] Specifically, the azo initiator is azobisisobutyronitrile.

[0078] The peroxide initiator is benzoyl peroxide and / or cumene hydroperoxide.

[0079] In the present invention, the molecular weight regulator includes one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, tetradecyl mercaptan, tridecyl mercaptan, undecyl mercaptan, and decyl mercaptan.

[0080] In some specific embodiments, the preparation process of the SAN resin further includes 5 to 25 parts of a solvent.

[0081] The solvent in the present invention can be selected with reference to the prior art, such as toluene, ethylbenzene, propylbenzene, acetonitrile, benzonitrile, and / or propionitrile.

[0082] The present invention also provides a method for preparing a SAN resin, comprising the following steps:

[0083] Mix the raw material components and carry out a polymerization reaction at 80 to 180 °C to remove volatiles to obtain the SAN resin.

[0084] The raw material components include an aromatic vinyl monomer, an alkenyl nitrile monomer, a molecular weight regulator, an initiator, and a solvent.

[0085] The polymerization reaction includes solution polymerization, bulk polymerization, or suspension polymerization.

[0086] In some specific embodiments, the time of the polymerization reaction is 1 to 3 hours.

[0087] In some specific embodiments, the other components include, but are not limited to, one or more of a filler, a reinforcing agent, a dye, a lubricant, a release agent, a stabilizer, an antioxidant, a UV absorber, a plasticizer, an impact modifier, an antistatic agent, a flame retardant, a bactericide, or a foaming agent.

[0088] Specifically, the filler or reinforcing agent includes, but is not limited to, one or more of silicate, amorphous silica, calcium silicate, quartz, mica, metal oxide, metal hydroxide, graphite, barium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, carbon fiber, or glass fiber.

[0089] Specifically, the pigment includes, but is not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide, or carbon black.

[0090] Specifically, the stabilizer includes, but is not limited to, one or more of m-phenylenediamine, salicylate, benzotriazole, or benzophenone.

[0091] Specifically, the release agent includes, but is not limited to, fatty acids having 12 to 30 carbon atoms, their salts and their derivatives, or polyolefin waxes, such as stearic acid, stearate, palmitic acid, palmitate, stearyl alcohol, amide wax, etc.

[0092] In the present invention, common antioxidants can be selected according to the prior art, such as but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants or thioester antioxidants.

[0093] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate or spiroglycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0094] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0095] Specifically, the thioester antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol tetrakis(3-laurylthiopropionate).

[0096] In the present invention, common lubricants can be selected according to the prior art, such as but not limited to at least one of amide lubricants, stearate lubricants, ester lubricants or silicone lubricants.

[0097] The present invention also provides a method for preparing an ABS resin composition, comprising the following steps:

[0098] Mixing the raw material components including the graft copolymer and the SAN resin evenly in proportion, feeding them into an extruder, and obtaining the product through melt blending and extrusion granulation.

[0099] The present invention also provides the application of the ABS resin composition in preparing automotive accessories and home appliance housing materials.

[0100] Compared with the prior art, the present invention has the following beneficial effects:

[0101] In the present invention, the provided ABS resin composition comprises a graft copolymer, a SAN resin and a functional group-substituted tetralin compound, and the functional group is one or more of a tertiary carbon, a quaternary carbon, an unsaturated carbon, a secondary amine or a tertiary amine group. The content of the functional group-substituted tetralin compound in the ABS resin composition is 200-3200 ppm. The ABS resin composition has excellent mechanical properties. Specific Embodiments

[0102] The present invention will be further elaborated below in conjunction with specific embodiments. The embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the test methods used in the following embodiments are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, are reagents and materials that can be obtained from commercial channels.

[0103] Raw materials used in each example and comparative example:

[0104] Polyconjugated diene latex: polybutadiene emulsion, solid content 50 ± 1%, self-made;

[0105] The specific preparation method is as follows:

[0106] 100 g of water, 100 g of butadiene monomer, 5 g of potassium rosin soap, 4 g of potassium carbonate, 0.3 g of tert-dodecyl mercaptan, and 0.3 g of potassium persulfate were added to a high-pressure stainless steel reactor. The reaction temperature was controlled at 65 °C and maintained for 30 hours. When the conversion rate exceeded 90%, diethylhydroxylamine was added to terminate the reaction to obtain a polybutadiene emulsion.

[0107] Styrene: 99%, 10 - 15 ppm TBC, purchased from Macklin;

[0108] Acrylonitrile: 99%, 10 - 15 ppm MEHQ, purchased from Macklin;

[0109] Functionally substituted tetrahydronaphthalene compounds:

[0110] Functionally substituted tetrahydronaphthalene compound 1: CAS No.: 57964-39-3, purchased from CATO;

[0111] Functionally substituted tetrahydronaphthalene compound 2: CAS No.: 26681-79-8, purchased from Wako;

[0112] Functionally substituted tetrahydronaphthalene compound 3: CAS No.: 91562-48-0, purchased from Apinno;

[0113] Functionally substituted tetrahydronaphthalene compound 4: CAS No.: 2510-03-4, purchased from Sigma-aldrich;

[0114] Functionally substituted tetrahydronaphthalene compound 5: CAS No.: 57964-40-6, purchased from CATO;

[0115] Functionally substituted tetrahydronaphthalene compound 6: CAS number: 59604-96-5, purchased from Maclean;

[0116] Functional group substituted tetralin compound 7: CAS number: 948006-26-6, purchased from Yuanye;

[0117] Functional group substituted tetralin compound 8: CAS number: 218903-61-8, purchased from LeYan;

[0118] Functional group substituted tetralin compound 9: CAS number: 1042797-88-5, purchased from LeYan;

[0119] Methyl substituted tetralin compounds: CAS number: 119-64-2, purchased from Aladdin;

[0120] Initiator:

[0121] Cumene hydroperoxide, commercially available;

[0122] Azobisisobutyronitrile, commercially available;

[0123] Activator:

[0124] Ferrous sulfate, potassium pyrophosphate and glucose are prepared in a molar ratio of 1:4:2, and all raw materials are commercially available;

[0125] Emulsifier: potassium oleate, commercially available;

[0126] Molecular weight regulator: tert-dodecyl mercaptan, commercially available; it should be noted that the raw materials used in the parallel experiments of the embodiment and the comparative example are the same commercially available products;

[0127] Examples 1 to 9

[0128] In Examples 1 to 9, the preparation method of the graft copolymer is as follows:

[0129] 200 parts by weight of a polybutadiene emulsion, 14 parts by weight of acrylonitrile, 41 parts by weight of styrene, 0.15 part by weight of cumene hydroperoxide, 1.6 parts by weight of an activator, 0.2 part by weight of a molecular weight regulator, 3 parts by weight of an emulsifier, and 0.3 part by weight of a tetrahydronaphthalene compound substituted with a functional group of the structure shown in Formula I were added to a sealed reaction kettle purged with nitrogen. After mixing evenly, a staged temperature-rising reaction was carried out. Specifically: the temperature of the first-stage reaction was 50 °C and the reaction time was 30 min; the temperature of the second-stage reaction was 55 °C and the reaction time was 240 min; the temperature of the third-stage reaction was 80 °C and the reaction time was 100 min, and then a graft copolymer was obtained through coagulation, dehydration, and drying; Examples 1 to 9 respectively used tetrahydronaphthalene compounds substituted with functional groups 1 to tetrahydronaphthalene compounds substituted with functional groups 9.

[0130] Example 10

[0131] The preparation method was the same as that of Example 1, except that 0.7 part of the tetrahydronaphthalene compound substituted with a functional group 1 was used entirely.

[0132] Examples 11 to 19

[0133] In Examples 11 to 19, the preparation method of the SAN resin was as follows:

[0134] 25 parts by weight of acrylonitrile and 75 parts by weight of styrene were added to 15 parts by weight of ethylbenzene, and 0.3 part by weight of a molecular weight regulator, 0.1 part by weight of a tetrahydronaphthalene compound substituted with a functional group of the structure shown in Formula I, and 0.01 part by weight of azobisisobutyronitrile were added to a sealed reaction kettle purged with nitrogen. The temperature was raised to 135 °C to start the polymerization reaction, and the reaction was carried out for 2 hours. After the polymerization was completed, it was transferred to a devolatilization kettle for devolatilization to obtain the SAN resin; Examples 11 to 19 respectively used tetrahydronaphthalene compounds substituted with functional groups 1 to tetrahydronaphthalene compounds substituted with functional groups 9.

[0135] Example 20

[0136] The preparation method was the same as that of Example 11, except that 0.11 part of the tetrahydronaphthalene compound substituted with a functional group 1 was used entirely.

[0137] Comparative Example 1

[0138] The preparation method was the same as that of Example 1, except that in Comparative Example 1, a methyl-substituted tetrahydronaphthalene compound was selected to replace the tetrahydronaphthalene compound substituted with a functional group 1 in an equal amount.

[0139] Comparative Example 2

[0140] The preparation method was the same as that of Example 1, except that in Comparative Example 2, 0.7 part of cumene hydroperoxide was used entirely.

[0141] Comparative Example 3

[0142] The preparation method is the same as that of Example 1, except that in Comparative Example 3, 3 parts by weight of the functional group-substituted tetralin compound 1 and 0.15 part by weight of cumene hydroperoxide are used.

[0143] Comparative Example 4

[0144] The preparation method is the same as that of Example 1, except that in Comparative Example 4, 0.01 part by weight of the functional group-substituted tetralin compound 1 and 0.7 part by weight of cumene hydroperoxide are used.

[0145] Comparative Example 5

[0146] The preparation method is the same as that of Example 11, except that in Comparative Example 5, the methyl-substituted tetralin compound is used in an equal amount to replace the functional group-substituted tetralin compound 1.

[0147] Comparative Example 6

[0148] The preparation method is the same as that of Example 11, except that in Comparative Example 6, 0.11 part by weight of azobisisobutyronitrile is used entirely.

[0149] Comparative Example 7

[0150] The preparation method is the same as that of Example 11, except that in Comparative Example 7, 0.5 part by weight of the functional group-substituted tetralin compound 1 and 0.01 part by weight of azobisisobutyronitrile are used.

[0151] Comparative Example 8

[0152] The preparation method is the same as that of Example 1, except that in Comparative Example 8, 0.02 part by weight of the functional group-substituted tetralin compound 1 and 0.01 part by weight of azobisisobutyronitrile are used.

[0153] Comparative Example 9

[0154] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Petrochemical Co., Ltd., Korea) and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly and melt-extruded to obtain an ABS resin composition, which is Comparative Example 9.

[0155] Examples 21 to 30 and Comparative Examples 10 to 13

[0156] 25 parts by weight of the graft copolymer prepared in the example / comparative example and 75 parts by weight of the SAN resin prepared in the example / comparative example were mixed evenly and melt-extruded to obtain an ABS resin composition, as shown in Tables 1 and 2 specifically:

[0157] Table 1 Formulations in Examples 21 to 30 (unit: part by weight)

[0158]

[0159]

[0160] Table 2 Formulations in Comparative Examples 10 to 13 (unit: parts by weight)

[0161]

[0162] Performance test:

[0163] Perform performance tests on the products prepared in the above examples and comparative examples. The specific test items and test methods are as follows:

[0164] 1. Test method:

[0165] (1) Determination of the graft copolymer conversion rate P: Take 0.75 - 1.5 g of the graft copolymer and dry it in an oven at 130 °C for 30 min to obtain the solid content B (wt / %) of the graft copolymer latex.

[0166] P 接枝共聚物 =(B·m 总 -m 助剂 -A·m 胶 ) / m 单体

[0167] In the formula, the sum of the masses of all raw material feedstocks is m 总 , the sum of the masses of the monomers is m 单体 , the mass of the diene latex is m 胶 , the solid content of the diene latex is A (wt / %), the sum of the masses of the non-monomer additives is m 助剂 , the solid content of the graft copolymer latex is B (wt / %), and P 接枝共聚物 is the graft conversion rate.

[0168] (2) The method for determining the monomer conversion rate of SAN resin polymerization is as follows:

[0169] P SAN =(m 聚合物 -m 助剂 ) / m 单体

[0170] In the formula, the sum of the masses of the monomers is m 单体 , the mass of the obtained SAN resin is counted as m 聚合物 , the sum of the masses of the additives is m 助剂 , and P SAN is the monomer conversion rate of SAN resin polymerization.

[0171] (3) Mechanical property test: Test the ABS resin compositions prepared in the above examples and comparative examples according to the standard of GB / T12672 - 2009.

[0172] (4) Measurement of weight-average molecular weight: The weight-average molecular weight of free SAN and the weight-average molecular weight of SAN resin were both determined by gel permeation chromatography. The mobile phase was tetrahydrofuran, the test temperature was 40 °C, the flow rate was 0.5 mL / min, the standard sample was polystyrene, and the chromatographic column model was pl-mixed-c;

[0173] Pretreatment of SAN resin: Take a small amount of SAN resin and dissolve it in tetrahydrofuran for 12 h, and filter it through a microporous filter into a sample injection bottle;

[0174] Pretreatment of graft copolymer: Take a small amount of graft copolymer and swell it in acetone, keep it at a constant temperature of 55 °C and shake it for 8 h, transfer it to a high-speed centrifuge tube, centrifuge it at 20000 rpm for 5 min, take the supernatant and filter it. After the solvent evaporates to dryness, take a quantitative amount of free SAN, dissolve it in tetrahydrofuran for 12 h, and filter it through a microporous filter into a sample injection bottle, that is, measure the weight-average molecular weight of free SAN in the graft copolymer; It should be noted that the molecular weight of the graft copolymer cannot be measured, and the molecular weight of the graft copolymer is reflected by measuring the weight-average molecular weight of free SAN.

[0175] (5) Determination of the content of functional group-substituted tetralin compounds:

[0176] a) Preparation of test sample, blank solution and external standard sample solution

[0177] Preparation of test sample: Take a small amount of graft copolymer or SAN resin or ABS resin composition and immerse it in liquid nitrogen for freezing for 2 min, transfer it to a mechanical grinder and grind it into a powder to obtain a frozen ground powder sample; Take a quantitative filter paper and record the weight of the filter paper, weigh 1.0000 g ± 1% of the frozen ground powder sample in the center of the filter paper, and fold the sample into the filter paper for internal wrapping. Place the sample in a Soxhlet extractor, use HPLC-grade methanol in the flask, extract at 85 °C for 48 h, and the obtained extract is filtered through a 0.22 μm filter for standby;

[0178] Preparation of blank solution: Place the blank filter paper in a Soxhlet extractor, extract with HPLC-grade methanol at 85 °C for 48 h, and the obtained extract is filtered through a 0.22 μm filter for standby;

[0179] Preparation of external standard sample solution: Take an appropriate amount of external standard sample (functional group-substituted tetralin compounds 1-9), and dilute it to 10 mg / L with HPLC-grade methanol;

[0180] b) Content test of functional group-substituted tetralin compounds

[0181] The content of the functional group-substituted tetrahydronaphthalene compound was tested by HPLC. The chromatogram was recorded and the content was calculated by the external standard method. The detection equipment was Waters ACQUITY Arc LC; the detector was Waters 2998 photodiode array detector, and the monitoring range was 190 - 400 nm; the chromatographic column model was Multospher "120RP 18HP 5μm, 250×2mm, mobile phase A: 0.01% formic acid aqueous solution by volume, mobile phase B: methanol, the sample injection volume was 10 μL; the column oven temperature was 50 °C; the mobile phase flow rate was 0.2 mL / min; the separation gradient was that mobile phase B increased from 40% to 100% within 40 minutes and was maintained for 10 minutes, and was equilibrated with 40% B for 15 minutes (specifically, eluted continuously in 40% mobile phase B and 60% mobile phase A by volume for 15 minutes).

[0182] 2. Test Results

[0183] The test results of each example and comparative example are shown in Tables 3 - 4.

[0184] Table 3 Conversion Rates and Weight-Average Molecular Weights of Each Graft Copolymer and SAN Resin

[0185]

[0186]

[0187]

[0188] Table 4 Mechanical Properties of ABS Resin Compositions of Examples 21 - 30 and Comparative Examples 9 - 13

[0189]

[0190]

[0191] As can be seen from Tables 3 - 4, from the test results of Examples 21 - 30 and Comparative Example 9, it can be known that the performance of the ABS resin composition containing the functional group-substituted tetrahydronaphthalene compound is better, the impact strength is better, and the performance is superior to the ABS resin composition prepared from the commercially available and excellent comprehensive performance KFA-130 resin and HR181 high rubber powder.

[0192] Obviously, the above examples of the present invention are merely illustrations for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. An ABS resin composition comprising a graft copolymer and a SAN resin, characterized in that, The content of the functional group-substituted tetralin represented by the formula I in the ABS resin composition is 200 to 3200 ppm; Among them, at least one of A to H is a functional substituent, and the functional substituent includes one or more of an ester group, a tertiary carbon, a quaternary carbon, an unsaturated carbon, a secondary amine or a tertiary amine; Preferably, the tertiary carbon includes -CH((CH2) x R)((CH2) y R); the quaternary carbon includes -C((CH2) x R)((CH2) y R)((CH2) z R); the unsaturated carbon includes -(CH2) x CN, =CH(CH2) x R, =C((CH2) x R))((CH2) y R); the secondary amine includes -NH(CH2) x R; the tertiary amine includes -N((CH2) x R))((CH2) y R); the ester group includes -COO(CH2) x R; x, y, and z in the functional substituent each independently selected from any integer value from 0 to 15; Each R is independently selected from hydrogen, methyl, amino, cyano, phenyl, hydroxyl, -COOR2, -COR2, carboxyl or aldehyde group; R2 is a straight-chain or branched-chain alkane having 0 to 18 carbon atoms.

2. The ABS resin composition according to claim 1, wherein The ABS resin composition comprises the following components calculated by weight: Graft copolymer 15 to 45 parts; SAN resin 55 to 85 parts; Other components 0 to 2 parts; The content of the functional group-substituted tetralin represented by the formula I in the graft copolymer is 250 to 3200 ppm; and the content of the functional group-substituted tetralin represented by the formula I in the SAN resin is 200 to 2000 ppm.

3. The ABS resin composition according to claim 1 or 2, characterized in that A to D are each independently selected from -CH((CH2) x R)((CH2) y R), -(CH2) x CN, -C((CH2) x R)((CH2) y R)((CH2) z R), =CH(CH2) x R, =C((CH2) x R))((CH2) y R), -NH(CH2) x R, -N((CH2) x R))((CH2) y R), -CO(CH2) x R or -COO(CH2) x R; and / or E to H are each independently selected from -CH((CH2) x R)((CH2) y R), -C((CH2) x R)((CH2) y R)((CH2) z R), -NH(CH2) x R, -N((CH2) x R))((CH2) y R), -CO(CH2) x R or -COO(CH2) x R; Preferably, each of A to D is independently selected from one or more of cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, =C(CN)2, -CH2CN, -COOCH3, -NHCOCH3 or -COOCH2CH3; or Each of E to H is independently selected from one or more of cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, -CH2CN, -COOCH3, -NHCOCH3 or -COOCH2CH3.

4. The ABS resin composition according to claim 1, characterized in that, A to H also include non-functional substituents, and the non-functional substituents include one or more of hydroxyl, carboxyl, phenyl or amino.

5. The ABS resin composition according to any one of claims 1 to 4, characterized in that, The functional group-substituted tetralin compound is: one or more of 6. The ABS resin composition according to claim 1 or 2, characterized in that, The graft copolymer comprises 100 parts by weight of polyconjugated diene units and 30 to 80 parts by weight of graft monomer units; The polyconjugated diene comprises: (a): 50 to 100% by weight of monomer A1, and the monomer A1 is selected from at least one of butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, isoprene or pentadiene; (b): 0 to 10% by weight of at least one polyfunctional crosslinking monomer A2; the functionality of the polyfunctional crosslinking monomer A2 is greater than or equal to 2; (c): 0 to 50% by weight of other monomers A3, and the monomer A3 is selected from at least one of styrene, α-methylstyrene, C2-C4 alkylstyrene, acrylonitrile, methacrylonitrile, chloroprene, C1-C8 alkyl (meth)acrylate, alkylene glycol di(meth)acrylate and vinyl methyl ether; The graft monomer comprises: (d): 50 to 100% by weight of aryl vinyl monomer B1, and the aryl vinyl monomer B1 is selected from styrene, α-methylstyrene or a mixture of styrene and at least one selected from α-methylstyrene, p-methylstyrene and C1-C8 alkyl (meth)acrylate; (e): 0 to 50% by weight of monomer B2, wherein the monomer B2 is selected from acrylonitrile or a mixture of acrylonitrile and at least one selected from methacrylonitrile, acrylamide, vinyl methyl ether, acid anhydrides of unsaturated carboxylic acids, and imides of unsaturated carboxylic acids.

7. The ABS resin composition according to claim 6, wherein Based on 100 parts by weight of the solid content of the polyconjugated diene, the graft copolymer further contains 0.1 to 2 parts by weight of an initiator, 0.2 to 4 parts by weight of an activator, 0.1 to 1 part by weight of a molecular weight regulator, and 0.5 to 5 parts by weight of an emulsifier.

8. The ABS resin composition according to claim 1 or 2, characterized in that The method for preparing the graft copolymer comprises the following steps: Mix the raw material components including polyconjugated diene, graft monomers, and auxiliaries evenly and carry out a staged temperature-raising reaction, and obtain the graft copolymer through coagulation, dehydration, and drying; preferably, for the staged temperature-raising reaction, the temperature of the first-stage reaction is 50 to 75 °C, and the reaction time is 10 to 60 min; the temperature of the second-stage reaction is 55 to 80 °C, and the reaction time is 60 to 240 min; the temperature of the third-stage reaction is 60 to 60 °C, and the reaction time is 50 to 150 min.

9. The ABS resin composition according to claim 1 or 2, characterized in that, The SAN resin comprises the following monomer units: (a): 65 to 60% by weight of at least one aromatic vinyl monomer B1, wherein the aromatic vinyl monomer B1 is selected from styrene, α-methylstyrene, or a mixture of styrene and at least one selected from α-methylstyrene, p-methylstyrene, and C1-C8 alkyl (meth)acrylates; (b): 10 to 35% by weight of at least one monomer B2, wherein the monomer B2 is selected from acrylonitrile, methacrylonitrile, acrylamide, or a mixture of acrylonitrile and at least one other monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, acid anhydrides of unsaturated carboxylic acids, and imides of unsaturated carboxylic acids; (c): 0 to 10% by weight of at least one polyfunctional crosslinking monomer B3; the functionality of the polyfunctional crosslinking monomer B3 is greater than or equal to 2.

10. The ABS resin composition according to claim 9, characterized in that, The SAN resin further contains 0.01 to 0.5% by weight of a molecular weight regulator; 0 to 0.05% by weight of an initiator.

11. The ABS resin composition according to claim 1 or 2, characterized in that The method for preparing the SAN resin comprises the following steps: Mix the raw material components including monomers and a molecular weight regulator, carry out a polymerization reaction at 80 to 180 °C, and remove volatiles to obtain the SAN resin.

12. A method for preparing the ABS resin composition according to claim 1 or 2, characterized in that, Comprises the following steps: Mix the raw material components including the graft copolymer and the SAN resin evenly in proportion, and feed them into an extruder for melt blending and extrusion granulation to obtain.

13. Use of an ABS resin composition according to any one of claims 1 to 11 in the preparation of automotive accessories and home appliance housing materials.

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