ABS resin composition, preparation method therefor and use thereof

Abstract

Disclosed in the present invention are an ABS resin composition, a preparation method therefor and the use thereof. The ABS resin composition in the present invention comprises a graft copolymer, an SAN resin, and a tetrahydronaphthalene compound substituted with a functional group, wherein the functional group comprises 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 content of said tetrahydronaphthalene compound in the ABS resin composition is 200-3200 ppm. The ABS resin composition has excellent mechanical properties.

Description

ABS resin composition, its preparation method and application TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer materials, and more particularly relates to an ABS resin composition, its preparation method and application. BACKGROUND

[0002] Homopolymerization and multivariate copolymerization of styrene is a classic of free radical polymerization, which has a unique self-initiation mechanism and involves homopolymerization or copolymerization of various resins, such as polystyrene resin (PS), poly-alpha-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 the like.

[0003] Styrene-based rubber can be prepared in an emulsifier aqueous solution using peroxide or azo initiators. According to the Smith-Ewart kinetic model, the reaction rate is high in the constant speed polymerization stage (Interval II), but as it enters the deceleration polymerization stage (Interval III), the monomer droplets disappear, the monomer concentration in the aqueous phase decreases, and the reaction rate also gradually decreases. In the prior art, the conversion rate is improved by adding initiators at the end of the reaction, but the addition of excessive initiators not only has a limited improvement in the conversion rate, but also has a negative impact on the mechanical properties of the material due to a high degree of crosslinking or a low 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 initiators added in this system can improve the conversion rate to a certain extent, but it will also lead to a decrease in the molecular weight of the resin material and a negative impact on the impact performance of the material. SUMMARY

[0004] The present application aims to overcome the above-mentioned defects or shortcomings, and provides an ABS resin composition, which comprises a functional group-substituted tetrahydronaphthalene compound, wherein the functional group comprises 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-mentioned purpose, the present application realizes the technical scheme as follows:

[0006] An ABS resin composition, which comprises a graft copolymer and a SAN resin, and the content of the functional group-substituted tetrahydronaphthalene compound shown in formula I in the ABS resin composition is 200-3200 ppm.

[0007]

[0008] Formula I;

[0009] Wherein, at least one of A to H is a functional substituent, and the functional substituent includes one or more of ester group, carbonyl group, tertiary carbon, quaternary carbon, unsaturated carbon, secondary amine or tertiary amine;

[0010] Preferably, the tertiary carbon includes -CH((CH2)). x R)((CH2) y R); Quaternary carbons include -C((CH2)); x R)((CH2) y R)((CH2) z R); Unsaturated carbon includes -(CH2). x CN、=CH(CH2) x R = C((CH2) x R))((CH2) y R); secondary amines include -NH(CH2) x R; Tertiary amines include -N((CH2) x R))((CH2) y R); ester groups include -COO(CH2). x R; carbonyl groups include -CO(CH2) x R;

[0011] The x, y, and z of the functional substituents are each independently selected from any integer value from 0 to 15; preferably, they are selected from any integer value from 0 to 3.

[0012] R is independently selected from hydrogen, methyl, amino, cyano, phenyl, hydroxyl, -COOR2, -COR2, carboxyl or aldehyde; R2 is a straight-chain or branched alkane with 0 to 18 carbon atoms, preferably a straight-chain or branched alkane with 0 to 3 or 10 to 14 carbon atoms.

[0013] It should be noted that the content of the functionally substituted tetrahydronaphthalene shown in Formula I in the present invention is 200~3200 ppm, for example, 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. ppm, 1200ppm, 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm, 2100ppm, 2200ppm, 2300ppm, 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, 3100ppm or 3200ppm, or any range between the above values.

[0014] Further, the ABS resin composition comprises the following components in parts by weight:

[0015] 15-45 parts of graft copolymer;

[0016] 55-85 parts of SAN resin;

[0017] Other components: 0-2 parts;

[0018] The content of the functionally substituted tetrahydronaphthalene of Formula I in the graft copolymer is 250~3200 ppm; and the content of the functionally substituted tetrahydronaphthalene of Formula I in the SAN resin is 200~2000 ppm.

[0019] Specifically, the content of the functionally substituted tetrahydronaphthalene shown in Formula I in the graft copolymer is 250~3200 ppm, for example, 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. 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm, 2100ppm, 2200ppm, 2300ppm, 2400ppm, 2500ppm, 2600ppm, 2700ppm, 2800ppm, 2900ppm, 3000ppm, 3100ppm, or 3200ppm, or any range between the above values.

[0020] Specifically, the content of the tetrahydronaphthalene substituted with the functional group shown in Formula I in the SAN resin is 200~2000ppm, for example, but not limited to 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1100ppm, 1200ppm, 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm or 2000ppm, or any range between the above values.

[0021] Furthermore, A through 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

[0022] E~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;

[0023] Furthermore, A~D are each independently selected from one or more of the following: cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, =C(CN)2, -CH2CN, -COOCH3, -NHCOCH3, or -COOCH2CH3; or

[0024] E~H are each independently selected from one or more of the following: cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, -CH2CN, -COOCH3, -NHCOCH3, or -COOCH2CH3.

[0025] Furthermore, A to H also include non-functional substituents, which include one or more of hydroxyl, carboxyl, phenyl, or amino groups.

[0026] Furthermore, the tetrahydronaphthalene substituted with the functional group is:

[0027] , , , , , , , or One or more of them.

[0028] The graft copolymer is a graft copolymer of a conjugated diene polymer; further, the graft copolymer is a core-shell structure polymer comprising a conjugated diene polymer as the core and a copolymer comprising an aromatic vinyl monomer and an alkenyl nitrile monomer as the shell.

[0029] Furthermore, the graft copolymer comprises 100 parts by weight of polyconjugated diene units and 30-80 parts by weight of graft monomer units.

[0030] The polyconjugated diene comprises:

[0031] (a): 50 to 100% by weight of monomer A1, wherein monomer A1 is selected from at least one of butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, isoprene or isoprene;

[0032] Furthermore, the monomer A1 is butadiene and / or isoprene.

[0033] (b): 0 to 10% by weight of at least one multifunctional crosslinking monomer A2; the functionality of said multifunctional crosslinking monomer A2 is greater than or equal to 2;

[0034] Furthermore, the multifunctional crosslinking monomer A2 can be at least one of allyl methacrylate, allyl acrylate, divinylbenzene, diethylene glycol dimethacrylate, 3-(triallylsilyl)propyl acrylate, N-hydroxymethylacrylamide, diacetone acrylamide, divinyltetramethoxydisilane, or 1,4-bis(vinyldimethylsilyl)benzene.

[0035] Furthermore, the multifunctional crosslinking monomer A2 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate, or divinyltetramethoxydisilane.

[0036] (c): 0 to 50% by weight of other monomer A3, wherein monomer A3 is selected from at least one of styrene, α-methylstyrene, C2-C4 alkylstyrene, acrylonitrile, methacrylonitrile, chloroprene, C1-C8 alkyl acrylate, alkylene glycol-di(meth)acrylate and vinyl methyl ether;

[0037] Further, the monomer A3 is at least one of styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, or methyl methacrylate.

[0038] The graft monomer comprises:

[0039] (d): 50 to 100% by weight of aryl vinyl monomer B1, wherein 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 (meth)acrylate C1 to C8 alkyl esters; preferably, 60 to 90% by weight of aryl vinyl monomer B1;

[0040] Furthermore, the aryl vinyl monomer B1 is at least one of styrene, methyl acrylate, or methyl methacrylate.

[0041] (e): 0 to 50% by weight of monomer B2, wherein monomer B2 is selected from acrylonitrile or a mixture of acrylonitrile and at least one selected from methacrylonitrile, acrylamide, vinyl methyl ether, an anhydride of an unsaturated carboxylic acid and an imide of an unsaturated carboxylic acid; preferably, 10 to 40% by weight of monomer B2.

[0042] Furthermore, the monomer B2 is acrylonitrile and / or acrylamide.

[0043] The polyconjugated diene unit is obtained by polymerizing the above monomers A1, A2, and A3, and the polymerization includes emulsion polymerization. The polyconjugated diene is usually in the form of latex, and optional polyconjugated diene latexes include polybutadiene latex, poly2,3-dimethyl-1,3-butadiene latex, 2-ethyl-1,3-butadiene latex, polyisoprene latex, or polyisoprene latex.

[0044] Furthermore, the polyconjugated diene latex is polybutadiene latex and / or polybutadiene-styrene latex.

[0045] Specifically, the gel content of the polyconjugated diene latex is 40-95 wt%, preferably 65-80 wt%.

[0046] Specifically, the average particle size of the polyconjugated diene latex is 60~600nm.

[0047] The solid content of the polyconjugated diene latex is 35~60wt%.

[0048] The polyconjugated diene latex of the present invention can be obtained commercially or by self-production, and its source is not particularly limited.

[0049] In some specific embodiments, the graft copolymer, based on 100 parts by weight of solids of polyconjugated diene, further includes 0.1 to 2 parts by weight of initiator, 0.2 to 4 parts by weight of activator, 0.1 to 1 part by weight of molecular weight regulator and 0.25 to 2.5 parts by weight of emulsifier.

[0050] The solid component of the polyconjugated diene is the non-volatile component of polyconjugated diene latex.

[0051] The initiator described in this invention includes one or more of redox initiators, azo initiators, or peroxide initiators.

[0052] Specifically, the 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.

[0053] The azo initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, or azobisisobutyramidine hydrochloride.

[0054] The peroxide initiator is one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl peroxide, or methyl ethyl ketone peroxide.

[0055] Specifically, the redox initiator and activator are used in combination.

[0056] The activator described in this invention includes ferrous sulfate, a complexing agent, and an aqueous solution of a reducing sugar.

[0057] In some specific embodiments, the complexing agent includes one or more of aminocarboxylate, hydroxycarboxylate, organophosphonate, and phosphate.

[0058] The reducing sugars include one or more of glucose, lactose, fructose, galactose, and maltose.

[0059] The molecular weight regulators described in this invention include one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, tetradecyl mercaptan, tridecyl mercaptan, undecyl mercaptan, and decadecyl mercaptan.

[0060] The emulsifiers described in this invention include C8-C 20 One or more of the following: saturated or unsaturated fatty acids, disproportionated rosin, dodecylbenzene sulfonic acid, and potassium or sodium salts of dodecyl sulfonic acid.

[0061] This invention also provides a method for preparing a graft copolymer, which can be prepared by emulsion polymerization, and the preparation method includes the following steps:

[0062] The raw materials are mixed evenly and subjected to a staged heating reaction. After coagulation, dehydration and drying, a graft copolymer is obtained. The raw materials include polyconjugated diene, graft monomer, initiator, activator, molecular weight regulator and emulsifier.

[0063] Specifically, the staged heating reaction is as follows: the temperature of the first stage reaction is 50~75℃ and the reaction time is 10~60 min; the temperature of the second stage reaction is 55~80℃ and the reaction time is 60~240 min; and the temperature of the third stage reaction is 60~90℃ and the reaction time is 50~150 min.

[0064] The present invention also discloses a SAN resin, wherein the SAN resin is a copolymer comprising an aromatic vinyl monomer and an alkenyl nitrile monomer.

[0065] Furthermore, the SAN resin comprises the following monomer units:

[0066] (a): 65-90% by weight of at least one aromatic monomer B1, wherein the 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 (meth)acrylate C1-C8 alkyl ester; preferably, 70-80 parts by weight of at least one aromatic monomer B1;

[0067] Furthermore, the aryl vinyl monomer B1 is at least one of styrene, methyl acrylate, or methyl methacrylate.

[0068] (b): 10-35% 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, anhydride of unsaturated carboxylic acids and imide of unsaturated carboxylic acids; preferably, 20-30 parts by weight of at least one monomer B2.

[0069] Furthermore, the monomer B2 is acrylonitrile and / or acrylamide.

[0070] (c): 0 to 10% by weight of at least one multifunctional crosslinking monomer B3; wherein the functionality of the multifunctional crosslinking monomer B3 is greater than or equal to 2.

[0071] Specifically, the multifunctional crosslinking monomer B3 is selected from at least one of allyl methacrylate, allyl acrylate, divinylbenzene, diethylene glycol dimethacrylate, 3-(triallylsilyl)propyl acrylate, N-hydroxymethylacrylamide, diacetone acrylamide, divinyltetramethoxydisilane, or 1,4-bis(vinyldimethylsilyl)benzene.

[0072] Furthermore, the multifunctional crosslinking monomer B3 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate, or divinyltetramethoxydisilane.

[0073] The SAN resin is obtained by copolymerization of the above-mentioned B1, B2, and B3 monomers, and the copolymerization includes random copolymerization, alternating copolymerization, syndiotactic copolymerization, or block copolymerization.

[0074] Furthermore, the copolymerization is achieved through emulsion polymerization. In some specific embodiments, the SAN resin further includes 0-0.5% by weight of an initiator and 0.01-0.5% by weight of a molecular weight regulator.

[0075] Other initiators described in this invention include azo initiators or peroxide initiators.

[0076] Specifically, the azo initiator is azobisisobutyronitrile.

[0077] The peroxide initiator is benzoyl peroxide and / or cumene hydroperoxide.

[0078] The molecular weight regulators described in this invention include one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, tetradecyl mercaptan, tridecyl mercaptan, undecyl mercaptan, and decadecyl mercaptan.

[0079] In some specific embodiments, the preparation process of the SAN resin also includes 5 to 25 parts of solvent.

[0080] The solvents described in this invention can be selected with reference to existing technologies, such as toluene, ethylbenzene, propylbenzene, formonitrile, acetonitrile, and / or propionitrile.

[0081] This invention also provides a method for preparing SAN resin, comprising the following steps:

[0082] The raw material components are mixed and polymerized at 80~180℃ to remove volatiles and obtain SAN resin.

[0083] The raw material components include aryl vinyl monomers, alkenyl nitrile monomers, molecular weight regulators, initiators, and solvents.

[0084] The polymerization reaction includes solution polymerization, bulk polymerization, or suspension polymerization.

[0085] In some specific embodiments, the polymerization reaction takes 1 to 3 hours.

[0086] In some specific embodiments, the other components include, but are not limited to, one or more of the following: fillers, reinforcing agents, dyes, lubricants, mold release agents, stabilizers, antioxidants, UV absorbers, plasticizers, impact modifiers, antistatic agents, flame retardants, bactericides, or foaming agents.

[0087] Specifically, the filler or reinforcing agent includes, but is not limited to, one or more of the following: silicates, amorphous silica, calcium silicate, quartz, mica, metal oxides, metal hydroxides, graphite, barium sulfate, calcium carbonate, magnesium carbonate, talc, kaolin, carbon fiber, or glass fiber.

[0088] Specifically, the pigments include, but are not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide, or carbon black.

[0089] Specifically, the stabilizer includes, but is not limited to, one or more of resorcinol diphenyl, salicylate, benzotriazole or benzophenone.

[0090] Specifically, the release agent includes, but is not limited to, fatty acids having 12 to 30 carbon atoms, their salts and derivatives, or polyolefin waxes, such as stearic acid, stearate, palmitic acid, palmitate, stearyl alcohol, amide wax, etc.

[0091] In this invention, commonly used antioxidants can be selected according to existing technology, such as, but not limited to, one or more of hindered phenolic antioxidants, phosphite antioxidants, or thioester antioxidants.

[0092] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, or spiroethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0093] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or bis(2,6-di-tert-butyl-4-tolyl) pentaerythritol phosphite.

[0094] Specifically, the thioester antioxidant is one or more of distearate thiodipropionate, dilaurate thiodipropionate, or pentaerythritol-based dodecathiopropyl ester.

[0095] In this invention, commonly used lubricants can be selected according to existing technology, such as, but not limited to, at least one of amide lubricants, stearate lubricants, ester lubricants or silicone lubricants.

[0096] The present invention also provides a method for preparing an ABS resin composition, comprising the following steps:

[0097] The raw material components, including graft copolymer and SAN resin, are mixed evenly in proportion, fed into an extruder, and obtained by melt blending and extrusion granulation.

[0098] The present invention also provides the application of the ABS resin composition in the preparation of automotive trim and appliance housing materials.

[0099] Compared with the prior art, the present invention has the following beneficial effects:

[0100] This invention provides an ABS resin composition comprising a graft copolymer, a SAN resin, and a functionally substituted tetrahydronaphthalene compound, wherein the functional group is one or more of a tertiary carbon, quaternary carbon, unsaturated carbon, secondary amine, or tertiary amine group. The content of the functionally substituted tetrahydronaphthalene compound in the ABS resin composition is 200-3200 ppm. The ABS resin composition exhibits excellent mechanical properties. Embodiments of the present invention

[0101] The present invention will be further described in detail below with reference to specific embodiments. These 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 experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0102] Raw materials used in each embodiment and comparative example:

[0103] Polyconjugated diene latex: Polybutadiene latex, solid content 50±1%, self-made;

[0104] The specific preparation method is as follows:

[0105] 100g water, 100g butadiene monomer, 5g rosin potassium salt, 4g potassium carbonate, 0.3g tert-dodecyl mercaptan, and 0.3g potassium persulfate were added to a high-pressure stainless steel reactor. The reaction temperature was controlled at 65℃ for 30 hours. When the conversion rate exceeded 90%, diethylhydroxylamine was added to stop the reaction and obtain polybutadiene emulsion.

[0106] Styrene: 99%, 10-15 ppm TBC, purchased from Macklin;

[0107] Acrylonitrile: 99%, 10-15 ppm MEHQ, purchased from Macklin;

[0108] Tetrahydronaphthalene compounds with functional group substitution:

[0109] Functionally substituted tetrahydronaphthalene compound 1: CAS No.: 57964-39-3, purchased from CATO;

[0110] Functionally substituted tetrahydronaphthalene compound 2: CAS No.: 26681-79-8, purchased from Wako;

[0111] 3. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 91562-48-0, purchased from Apinno;

[0112] 4. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 2510-03-4, purchased from Sigma-aldrich;

[0113] 5. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 57964-40-6, purchased from CATO;

[0114] Functionally substituted tetrahydronaphthalene compounds 6: CAS No.: 59604-96-5, purchased from McLean;

[0115] 7. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 948006-26-6, purchased from Yuanye;

[0116] 8. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 218903-61-8, purchased from Leyan;

[0117] 9. Tetrahydronaphthalene compounds with functional group substitution: CAS No.: 1042797-88-5, purchased from Leyan;

[0118] Methyl-substituted tetrahydronaphthalene compounds: CAS No.: 119-64-2, purchased from Aladdin;

[0119] Initiator:

[0120] Cumene hydroperoxide, commercially available;

[0121] Azobisisobutyronitrile (AIBN), commercially available;

[0122] Activator:

[0123] The mixture was prepared by combining ferrous sulfate, potassium pyrophosphate, and glucose in a molar ratio of 1:4:2. All raw materials were commercially available.

[0124] Emulsifier: Potassium oleate, commercially available;

[0125] Molecular weight regulator: tert-dodecyl mercaptan, commercially available; it should be noted that the raw materials used in the parallel experiments of the examples and comparative examples were the same commercially available products.

[0126] Examples 1-9

[0127] In Examples 1-9, the graft copolymers were prepared using the following methods:

[0128] 200 parts by weight of polybutadiene emulsion, 14 parts by weight of acrylonitrile, 41 parts by weight of styrene, 0.15 parts by weight of cumene hydroperoxide, 1.6 parts by weight of activator, 0.2 parts by weight of molecular weight regulator, 3 parts by weight of emulsifier, and 0.3 parts by weight of tetrahydronaphthalene compound with functional group substitution of the structure shown in Formula I were added to a sealed reactor after nitrogen purging. After mixing evenly, a staged heating 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. Then, after coagulation, dehydration, and drying, the graft copolymer was obtained. Examples 1 to 9 used tetrahydronaphthalene compound 1 to tetrahydronaphthalene compound 9 with functional group substitution, respectively.

[0129] Example 10

[0130] The preparation method is the same as in Example 1, except that all of them use tetrahydronaphthalene compound 1 with 0.7 parts of functional group substitution.

[0131] Examples 11-19

[0132] In Examples 11-19, the preparation method of the SAN resin is as follows:

[0133] 25 parts by weight of acrylonitrile and 75 parts by weight of styrene were added to 15 parts by weight of ethylbenzene, along with 0.3 parts by weight of a molecular weight regulator, 0.1 parts by weight of a functionally substituted tetrahydronaphthalene compound with the structure shown in Formula I, and 0.01 parts by weight of azobisisobutyl nitrile. The mixture was then placed in a sealed reactor purged with nitrogen. The temperature was raised to 135°C to begin the polymerization reaction, which lasted for 2 hours. After polymerization, the mixture was transferred to a devolatilization reactor for devolatilization to obtain SAN resin. Examples 11-19 used functionally substituted tetrahydronaphthalene compound 1 to functionally substituted tetrahydronaphthalene compound 9, respectively.

[0134] Example 20

[0135] The preparation method is the same as in Example 11, except that all of them are tetrahydronaphthalene compounds 1 with functional group substitutions, with 0.11 parts by weight.

[0136] Comparative Example 1

[0137] The preparation method is the same as in Example 1, except that in Comparative Example 1, a methyl-substituted tetrahydronaphthalene compound is used to replace the functional group-substituted tetrahydronaphthalene compound 1 in equal amounts.

[0138] Comparative Example 2

[0139] The preparation method is the same as in Example 1, except that in Comparative Example 2, 0.7 parts by weight of cumene hydroperoxide were used throughout.

[0140] Comparative Example 3

[0141] The preparation method is the same as in Example 1, except that in Comparative Example 3, 3 parts by weight of tetrahydronaphthalene compound 1 with functional group substitution and 0.15 parts by weight of cumene hydroperoxide are used.

[0142] Comparative Example 4

[0143] The preparation method is the same as in Example 1, except that in Comparative Example 4, 0.01 parts by weight of tetrahydronaphthalene compound 1 with functional group substitution and 0.7 parts by weight of cumene hydroperoxide are used.

[0144] Comparative Example 5

[0145] The preparation method is the same as in Example 11, except that in Comparative Example 5, a methyl-substituted tetrahydronaphthalene compound is used to replace the functional group-substituted tetrahydronaphthalene compound 1 in equal amounts.

[0146] Comparative Example 6

[0147] The preparation method is the same as in Example 11, except that in Comparative Example 6, 0.11 parts by weight of azobisisobutyl nitrile were used throughout.

[0148] Comparative Example 7

[0149] The preparation method is the same as in Example 11, except that in Comparative Example 7, 0.5 parts by weight of tetrahydronaphthalene compound 1 with functional group substitution and 0.01 parts by weight of azobisisobutyl nitrile were used.

[0150] Comparative Example 8

[0151] The preparation method is the same as in Example 1, except that in Comparative Example 8, 0.02 parts by weight of tetrahydronaphthalene compound 1 with functional group substitution and 0.01 parts by weight of azobisisobutyl nitrile are used.

[0152] Comparative Example 9

[0153] 25 parts by weight of graft copolymer (ABS high-rubber powder, HR-181, Kumho Ilryk, South Korea) and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfeng) were mixed evenly and melt-extruded to obtain an ABS resin composition, which is Comparative Example 9.

[0154] Examples 21-30 and Comparative Examples 10-13

[0155] 25 parts by weight of the graft copolymer prepared in the examples / comparative examples were mixed with 75 parts by weight of the SAN resin prepared in the examples / comparative examples, and then melt-extruded to obtain ABS resin compositions, as shown in Tables 1 and 2:

[0156] Table 1. Formulations for Examples 21-30 (Unit: Parts by Weight)

[0157]

[0158] Table 2. Formulations for Comparative Examples 10-13 (Unit: parts by weight)

[0159]

[0160] Performance testing:

[0161] The products prepared in the above embodiments and comparative examples were subjected to performance tests. The specific test items and test methods are as follows:

[0162] 1. Testing method:

[0163] (1) Determination of graft copolymer conversion rate P: Take 0.75~1.5g of graft copolymer and dry it in an oven at 130℃ for 30 min to obtain the solid content B (wt / %) of graft copolymer latex.

[0164] P 接枝共聚物 =(B·m 总 -m 助剂 -A·m 胶 ) / m 单体

[0165] The sum of the masses of all raw materials in the formula is m. 总 The combined mass 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 / %), and the added mass of non-monomer additives is m. 助剂 The solid content of the graft copolymer latex is B (wt / %), P 接枝共聚物 The grafting conversion rate is denoted as .

[0166] (2) The method for determining the monomer conversion rate of SAN resin polymerization is as follows:

[0167] P SAN =(m 聚合物 -m 助剂 ) / m 单体

[0168] The sum of the monomers in the formula is m. 单体 The mass of the obtained SAN resin was m. 聚合物 The total mass of the additives is m. 助剂 P SAN The monomer conversion rate for SAN resin polymerization.

[0169] (3) Mechanical property test: The ABS resin compositions prepared in the above examples and comparative examples were tested in accordance with GB / T 12672-2009 standard.

[0170] (4) Weight-average molecular weight test: The weight-average molecular weight of free SAN and the weight-average molecular weight of SAN resin were determined by gel permeation chromatography. The mobile phase was tetrahydrofuran, the test temperature was 40℃, the flow rate was 0.5 mL / min, the standard sample was polystyrene, and the chromatographic column model was pl-mixed-c.

[0171] Pretreatment of SAN resin: Dissolve a small amount of SAN resin in tetrahydrofuran for 12 hours and filter it into a sample vial using microfiltration.

[0172] Pretreatment of graft copolymer: A small amount of graft copolymer was swollen in acetone and shaken at 55°C for 8 hours. The solution was then transferred to a high-speed centrifuge tube and centrifuged at 20,000 rpm for 5 minutes. The supernatant was collected and filtered. After the solvent evaporated, a quantitative amount of free SAN was collected, dissolved in tetrahydrofuran for 12 hours, and filtered through a micropore into a sample vial. This determined the weight-average molecular weight of the free SAN in the graft copolymer. It should be noted that the molecular weight of the graft copolymer cannot be measured directly. The molecular weight of the graft copolymer is reflected by measuring the weight-average molecular weight of the free SAN.

[0173] (5) Determination of the content of tetrahydronaphthalene compounds with functional group substitution:

[0174] a) Preparation of test samples, blank solutions and external standard sample solutions

[0175] Sample preparation: A small amount of graft copolymer, SAN resin, or ABS resin composition was immersed in liquid nitrogen and frozen for 2 minutes. It was then transferred to a mechanical grinder and ground into powder to obtain a cryogenically ground sample. A quantitative filter paper was taken, and its weight was recorded. 1.0000 g ± 1% of the cryogenically ground sample was placed in the center of the filter paper, and the sample was folded inside the filter paper. The sample was placed in a solenoid extractor and extracted at 85°C for 48 hours using HPLC-grade methanol in a flask. The resulting extract was filtered through a 0.22 μm filter for later use.

[0176] Preparation of blank solution: Place blank filter paper in a solenoid extractor and extract with HPLC-grade methanol at 85℃ for 48h. The resulting solenoid extract is filtered through 0.22μm and then used for later use.

[0177] Preparation of external standard sample solution: Take an appropriate amount of external standard sample (functionally substituted tetrahydronaphthalene compounds 1-9) and dilute it to 10 mg / L with HPLC-grade methanol;

[0178] b) Content testing of functionally substituted tetrahydronaphthalene compounds

[0179] The content of functionally substituted tetrahydronaphthalene compounds was determined by HPLC. Chromatograms were recorded, and the content was calculated using the external standard method. The detection equipment was a Waters ACQUITY Arc LC; the detector was a Waters 2998 photodiode array detector with a monitoring range of 190–400 nm; the column model was a Multospher" 120 RP 18 HP 5 μm, 250 × 2 mm; mobile phase A was 0.01% formic acid aqueous solution, and mobile phase B was methanol, with a loading volume of 10 μL; the column temperature was 50℃; the mobile phase flow rate was 0.2 mL / min; the separation gradient was: mobile phase B from 40% to 100% over 40 minutes, maintained for 10 minutes, and then equilibrated in 40% B for 15 minutes (specifically, elution was performed for 15 minutes in a mixture of 40% mobile phase B and 60% mobile phase A).

[0180] 2. Test Results

[0181] The test results of each embodiment and comparative example are shown in Tables 3-4.

[0182] Table 3 Conversion rate and weight-average molecular weight of each graft copolymer and SAN resin

[0183]

[0184] Table 4 Mechanical properties of the ABS resin compositions in Examples 21-30 and Comparative Examples 9-13

[0185]

[0186] As can be seen from Tables 3-4, the test results of Examples 21-30 and Comparative Example 9 show that the ABS resin composition containing tetrahydronaphthalene compounds with functional group substitution has better performance, better impact strength, and better performance than the commercially available KFA-130 resin and the ABS resin composition made from HR181 high-resin powder, which have excellent overall performance.

[0187] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection 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 tetrahydronaphthalene shown in Formula I in the ABS resin composition is 200~3200 ppm. Formula I; Wherein, at least one of A to H is a functional substituent, and the functional substituent includes one or more of ester group, tertiary carbon, quaternary carbon, unsaturated carbon, secondary amine or tertiary amine; Preferably, the tertiary carbon includes -CH((CH2)). x R)((CH2) y R); Quaternary carbons include -C((CH2)); x R)((CH2) y R)((CH2) z R); Unsaturated carbon includes -(CH2). x CN、=CH(CH2) x R = C((CH2) x R))((CH2) y R); secondary amines include -NH(CH2) x R; Tertiary amines include -N((CH2) x R))((CH2) y R); ester groups include -COO(CH2). x R; The x, y, and z in the functional substituents are each independently selected from any integer value from 0 to 15; R is independently selected from hydrogen, methyl, amino, cyano, phenyl, hydroxyl, -COOR2, -COR2, carboxyl or aldehyde; R2 is a straight-chain or branched alkane with 0 to 18 carbon atoms.

2. The ABS resin composition according to claim 1, characterized in that, The ABS resin composition comprises the following components in parts by weight: 15-45 parts of graft copolymer; 55-85 parts of SAN resin; Other components: 0-2 parts; The content of the functionally substituted tetrahydronaphthalene of Formula I in the graft copolymer is 250~3200 ppm; and the content of the functionally substituted tetrahydronaphthalene of Formula I in the SAN resin is 200~2000 ppm.

3. The ABS resin composition according to claim 1 or 2, characterized in that, A through 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~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, A to D are each independently selected from one or more of the following: cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, =C(CN)2, -CH2CN, -COOCH3, -NHCOCH3, or -COOCH2CH3; or E~H are each independently selected from one or more of the following: 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, which include one or more of hydroxyl, carboxyl, phenyl, or amino groups.

5. The ABS resin composition according to any one of claims 1 to 4, characterized in that, The functionally substituted tetrahydronaphthalene compound is: 、 、 、 、 、 、 、 or One or more of them.

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 30-80 parts by weight of graft monomer units. The polyconjugated diene comprises: (a): 50 to 100% by weight of monomer A1, wherein monomer A1 is selected from at least one of butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, isoprene or isoprene; (b): 0 to 10% by weight of at least one multifunctional crosslinking monomer A2; the functionality of said multifunctional crosslinking monomer A2 is greater than or equal to 2; (c): 0 to 50% by weight of other monomer A3, wherein monomer A3 is selected from at least one of styrene, α-methylstyrene, C2-C4 alkylstyrene, acrylonitrile, methacrylonitrile, chloroprene, C1-C8 alkyl 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, wherein 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 (meth)acrylate C1 to C8 alkyl esters; (e): 0 to 50% by weight of monomer B2, wherein monomer B2 is selected from acrylonitrile or a mixture of acrylonitrile and at least one selected from methacrylonitrile, acrylamide, vinyl methyl ether, an anhydride of an unsaturated carboxylic acid and an imide of an unsaturated carboxylic acid.

7. The ABS resin composition according to claim 6, characterized in that, The graft copolymer, based on 100 parts by weight of polyconjugated diene, further comprises 0.1 to 2 parts by weight of initiator, 0.2 to 4 parts by weight of activator, 0.1 to 1 part by weight of molecular weight regulator, and 0.5 to 5 parts by weight of emulsifier.

8. The ABS resin composition according to claim 1 or 2, characterized in that, The method for preparing the graft copolymer includes the following steps: The raw material components, including polyconjugated diene, graft monomer, and additives, are mixed uniformly and subjected to a staged heating reaction. After coagulation, dehydration, and drying, a graft copolymer is obtained. Preferably, the staged heating reaction is as follows: the temperature of the first stage reaction is 50~75℃, and the reaction time is 10~60 min; the temperature of the second stage reaction is 55~80℃, and the reaction time is 60~240 min; and the temperature of the third stage reaction is 60~90℃, and the reaction time is 50~150 min.

9. The ABS resin composition according to claim 1 or 2, characterized in that, The SAN resin comprises the following monomer units: (a): 65-90% by weight of at least one aromatic monomer B1, said aromatic monomer B1 being selected from styrene, α-methylstyrene, or a mixture of styrene and at least one selected from α-methylstyrene, p-methylstyrene and (meth)acrylate C1-C8 alkyl esters; (b): 10-35% 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, anhydride of unsaturated carboxylic acids and imide of unsaturated carboxylic acids; (c): 0 to 10% by weight of at least one multifunctional crosslinking monomer B3; wherein the functionality of the multifunctional 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 also contains 0.01 to 0.5% by weight of a molecular weight regulator and 0 to 0.05% by weight of an initiator.

11. The ABS resin composition according to claim 1 or 2, characterized in that, The preparation method of the SAN resin includes the following steps: The raw material components, including monomers and molecular weight regulators, are mixed and polymerized at 80-180°C to remove volatiles and obtain SAN resin.

12. A method for preparing the ABS resin composition as described in claim 1 or 2, characterized in that, Includes the following steps: The raw material components, including graft copolymer and SAN resin, are mixed evenly in proportion, fed into an extruder, and obtained by melt blending and extrusion granulation.

13. The use of an ABS resin composition as described in any one of claims 1 to 11 in the preparation of automotive trim and appliance housing materials.

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