Preparation method and application of graft copolymer as well as preparation method and application of ABS (Acrylonitrile Butadiene Styrene) resin composition containing graft copolymer

Abstract

The invention discloses a graft copolymer and a preparation method and application of an ABS resin composition containing the graft copolymer. The graft copolymer contains 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. When the functional group substituted tetrahydronaphthalene compound is used for synthesizing a grafted copolymer, a polymerization reaction can be initiated, the dosage of a traditional common initiator is reduced, the conversion rate is equivalent to that of a polymerization process using the traditional initiator, meanwhile, the molecular weight of the grafted copolymer is increased, the cleanliness of resin is increased, and the service life of the resin is prolonged. And the composition obtained by applying the prepared grafted copolymer has better mechanical properties.

Description

Technical Field

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

[0002] The homopolymerization and copolymerization of styrene are classical in free radical polymerization, with a unique self-initiating 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), etc.

[0003] Styrene-based rubber can be prepared in an aqueous solution of an emulsifier using peroxide or azo initiators. 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, the 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 improve 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-mentioned defects or deficiencies, and provide a graft copolymer containing a tetrahydronaphthalene compound substituted with a functional group, wherein 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. When the tetrahydronaphthalene compound substituted with a functional group is used in the synthesis of the graft copolymer, it can initiate the polymerization reaction, reduce the amount of traditional common initiators used, and when the same amount of initiator is added, the conversion rate is comparable, the molecular weight of the obtained graft copolymer is higher, the cleanliness of the resin is higher, and the mechanical properties of the ABS resin composition obtained from the prepared graft copolymer are better.

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

[0006] A graft copolymer, wherein the content of the tetrahydronaphthalene substituted with a functional group shown in Formula Ⅰ in the graft copolymer is 250 - 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 of 0 to 15; preferably selected from any integer value of 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 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.

[0013] 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) x R; and / or

[0014] 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;

[0015] Further, 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

[0016] 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.

[0017] Further, A to H further include non-functional substituents, and the non-functional substituents include one or more of hydroxyl, carboxyl, phenyl, or amino.

[0018] Still further, the tetrahydronaphthalene substituted with functional groups is:

[0019]

[0020] one or more of.

[0021] The graft copolymer is a graft copolymer of a conjugated diene polymer; further, the graft copolymer is a core-shell structure polymer having a conjugated diene polymer as the core and a copolymer including an aromatic vinyl monomer and an alkenyl nitrile monomer as the shell.

[0022] Further, the graft copolymer includes 100 parts by weight of polyconjugated diene units and 30 to 80 parts by weight of graft monomer units; the polyconjugated diene includes:

[0023] (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;

[0024] Further, the monomer A1 is butadiene and / or isoprene.

[0025] (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;

[0026] Further, the 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.

[0027] Furthermore, the polyfunctional crosslinking monomer A2 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate, or divinyltetramethoxydisilane.

[0028] (c): 0 to 50% by weight of other monomer A3, the monomer A3 being 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;

[0029] Further, the monomer A3 is at least one of styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, or methyl methacrylate.

[0030] The graft monomer comprises:

[0031] (d): 50 to 100% by weight of aryl vinyl monomer B1, the aryl vinyl monomer B1 being 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;

[0032] Further, the aryl vinyl monomer B1 is at least one of styrene, methyl acrylate, or methyl methacrylate.

[0033] (e): 0 to 50% by weight of monomer B2, the monomer B2 being selected from acrylonitrile or a mixture of acrylonitrile and at least one of methacrylonitrile, acrylamide, vinyl methyl ether, acid anhydride of unsaturated carboxylic acid, and imide of unsaturated carboxylic acid; preferably, 10 to 40% by weight of monomer B2.

[0034] Further, the monomer B2 is acrylonitrile and / or acrylamide.

[0035] The polyconjugated diene unit is obtained by polymerizing the above monomers A1, A2, and A3, and the polymerization includes emulsion polymerization. The polyconjugated diene usually exists in the form of latex, and optional polyconjugated diene latexes include polybutadiene latex, polybutadiene-styrene latex, polybutadiene-acrylonitrile latex, polybutadiene-methyl methacrylate latex, polybutadiene-acrylamide latex, poly-2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene latex, polyisoprene, or polymethylpentadiene latex.

[0036] Further, the polyconjugated diene latex is polybutadiene latex and / or polybutadiene-styrene latex.

[0037] Specifically, the gel content of the polyconjugated diene latex is 40 to 95 wt%, preferably 65 to 80 wt%.

[0038] Specifically, the average particle size of the polyconjugated diene latex is 60 to 600 nm.

[0039] The solid content of the polyconjugated diene latex is 35 to 60 wt%.

[0040] The polyconjugated diene latex of the present invention can be obtained commercially or prepared by oneself, and there is no special limitation on its source.

[0041] 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.

[0042] The solid content of the polyconjugated diene is the non-volatile content of the polyconjugated diene latex.

[0043] The initiator in the present invention includes one or more of redox initiators, azo initiators, or peroxide initiators.

[0044] 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.

[0045] The azo initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobis(isobutylamidine) hydrochloride, or azobis(isobutylimidazoline) hydrochloride.

[0046] The peroxide initiator is one or more of potassium persulfate, ammonium persulfate, benzoyl peroxide, tert-butyl benzoyl peroxide, or methyl ethyl ketone peroxide.

[0047] Specifically, the redox initiator and the activator are used in combination.

[0048] The activator in the present invention includes ferrous sulfate, a complexing agent, and an aqueous solution of a reducing sugar.

[0049] In some specific embodiments, the complexing agent includes one or more of aminocarboxylates, hydroxycarboxylates, organophosphonates, or phosphates.

[0050] The reducing sugar includes one or more of glucose, lactose, fructose, galactose, or maltose.

[0051] 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.

[0052] In the present invention, the emulsifier includes one or more of saturated or unsaturated fatty acids having C8-C 20 and disproportionated rosin, dodecylbenzenesulfonic acid, potassium salt or sodium salt of dodecylsulfonic acid.

[0053] 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:

[0054] Mix the raw materials evenly and carry out stepwise temperature-rising reaction, and obtain the graft copolymer through coagulation, dehydration and drying; the raw materials include polyconjugated diene, graft monomer, initiator, activator, molecular weight regulator and emulsifier.

[0055] Specifically, for the stepwise temperature-rising 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.

[0056] The present invention also provides an ABS resin composition, which includes the following components calculated by weight:

[0057] Graft copolymer: 15-45 parts;

[0058] SAN resin: 55-85 parts;

[0059] Other components: 0-2 parts.

[0060] Furthermore, the graft copolymer is partially or wholly a graft copolymer of tetrahydronaphthalene substituted with the functional group shown in Formula I.

[0061] Furthermore, the mass ratio of the graft copolymer of tetrahydronaphthalene substituted with the functional group shown in Formula I in the ABS resin composition to the graft copolymer can be 1-100%. For example, 2%, 5%, 10%, 25%, 50%, 75%, 95%, or the range between any of the above values.

[0062] Furthermore, the content of tetrahydronaphthalene substituted with the functional group shown in Formula I in the ABS resin composition is 75-1500 ppm.

[0063] The content of the functional group-substituted tetralin represented by Formula I in the ABS resin composition is 75 to 1500 ppm, for example but not limited to 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 ppm, 210 ppm, 220 ppm, 230 ppm, 240 ppm, 250 ppm, 260 ppm, 270 ppm, 280 ppm, 290 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm or 1500 ppm, or a range between any of the above values.

[0064] 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 mold release agent, a stabilizer, an antioxidant, a UV absorber, a plasticizer, an impact modifier, an antistatic agent, a flame retardant, a fungicide or a foaming agent.

[0065] 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.

[0066] Specifically, the pigment includes, but is not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide or carbon black.

[0067] Specifically, the stabilizer includes, but is not limited to, one or more of m-phenylene diphenol, salicylate, benzotriazole or benzophenone.

[0068] Specifically, the mold release agent includes, but is not limited to, a fatty acid having 12 to 30 carbon atoms, its salt and its derivatives, or a polyolefin wax, such as stearic acid, stearate, palmitic acid, palmitate, stearyl alcohol, amide wax, etc.

[0069] In the present invention, common antioxidants can be selected according to the prior art, for example but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants or thioester antioxidants.

[0070] Specifically, the hindered phenol antioxidant is one or more of N, N'-hexamethylenebis(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, n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, or spiroglycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0071] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0072] Specifically, the thioester antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate, or pentaerythritol tetrakis(3-laurylthiopropionate).

[0073] 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.

[0074] The present invention also provides a method for preparing an ABS resin composition, comprising the following steps:

[0075] Mixing the raw material components including the graft copolymer and the SAN resin in proportion and uniformly, feeding them into an extruder, and obtaining the product through melt blending and extrusion granulation.

[0076] The present invention also provides the application of the ABS resin composition in the preparation of automotive accessories and household appliance housing materials.

[0077] Compared with the prior art, the present invention has the following beneficial effects:

[0078] In the present invention, a graft copolymer is provided, which contains a tetrahydronaphthalene compound substituted with a functional group, 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. When the tetrahydronaphthalene compound substituted with a functional group is used in the synthesis of the graft copolymer, it can initiate the polymerization reaction, reduce the amount of traditional initiators, increase the molecular weight while achieving a comparable conversion rate, improve the resin cleanliness, and the mechanical properties of the composition obtained by applying the prepared graft copolymer are better; because the graft copolymer of the present invention has a higher molecular weight, the ABS resin composition prepared therefrom has higher mechanical properties. Detailed Embodiments

[0079] The present invention will be further elaborated in detail 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.

[0080] Raw materials used in each example and comparative example:

[0081] Polyconjugated diene latex: polybutadiene emulsion, solid content 50 ± 1%, self-made;

[0082] The specific preparation method is as follows:

[0083] 100 g of water, 100 g of butadiene monomer, 5 g of potassium rosinate, 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, and 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.

[0084] Styrene: 99%, 10 - 15 ppm TBC, purchased from Macklin;

[0085] Acrylonitrile: 99%, 10 - 15 ppm MEHQ, purchased from Macklin;

[0086] Functionally substituted tetrahydronaphthalene compounds:

[0087] Functionally substituted tetrahydronaphthalene compound 1: CAS No.: 57964-39-3, purchased from CATO;

[0088] Functionally substituted tetrahydronaphthalene compound 2: CAS No.: 26681-79-8, purchased from Wako;

[0089] Functionally substituted tetrahydronaphthalene compound 3: CAS No.: 91562-48-0, purchased from Apinno;

[0090] Functionally substituted tetrahydronaphthalene compound 4: CAS No.: 2510-03-4, purchased from Sigma-aldrich;

[0091] Functionally substituted tetrahydronaphthalene compound 5: CAS No.: 57964-40-6, purchased from CATO;

[0092] Functionally substituted tetrahydronaphthalene compound 6: CAS number: 59604-96-5, purchased from Maclean;

[0093] Functional group substituted tetralin compound 7: CAS number: 948006-26-6, purchased from Yuanye;

[0094] Functional group substituted tetralin compound 8: CAS number: 218903-61-8, purchased from LeYan;

[0095] Functional group substituted tetralin compound 9: CAS number: 1042797-88-5, purchased from LeYan;

[0096] Methyl substituted tetralin compounds: CAS number: 119-64-2, purchased from Aladdin;

[0097] Initiator:

[0098] Cumene hydroperoxide, commercially available;

[0099] Azobisisobutyronitrile, commercially available;

[0100] Activator:

[0101] Ferrous sulfate, potassium pyrophosphate and glucose are prepared in a molar ratio of 1:4:2, and all raw materials are commercially available;

[0102] Emulsifier: potassium oleate, commercially available;

[0103] 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;

[0104] Examples 1 to 9

[0105] In Examples 1 to 9, the preparation method of the graft copolymer is as follows:

[0106] 200 parts by weight of 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 activator, 0.2 part by weight of molecular weight regulator, 3 parts by weight of emulsifier, and 0.3 part by weight of a tetrahydronaphthalene compound substituted with a functional group 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.

[0107] Example 10

[0108] 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.

[0109] Comparative Example 1

[0110] The preparation method was the same as that of Example 1, except that in Comparative Example 1, a methyl-substituted tetrahydronaphthalene compound was used in an equal amount to replace the tetrahydronaphthalene compound substituted with a functional group 1.

[0111] Comparative Example 2

[0112] The preparation method was the same as that of Example 1, except that in Comparative Example 2, 0.7 part by weight of cumene hydroperoxide was used entirely.

[0113] Comparative Example 3

[0114] The preparation method was the same as that of Example 1, except that in Comparative Example 3, 3 parts by weight of the tetrahydronaphthalene compound substituted with a functional group 1 and 0.15 part by weight of cumene hydroperoxide were used.

[0115] Comparative Example 4

[0116] The preparation method was the same as that of Example 1, except that in Comparative Example 4, 0.01 part by weight of the tetrahydronaphthalene compound substituted with a functional group 1 and 0.7 part by weight of cumene hydroperoxide were used.

[0117] Examples 11 to 20 and Comparative Examples 5 to 8

[0118] 25 parts by weight of the graft copolymers prepared in Examples 1 to 10 and Comparative Examples 1 to 4 and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly and melt-extruded to obtain an ABS resin composition. The ABS resin compositions corresponding to Examples 1 to 10 and Comparative Examples 1 to 4 were respectively denoted as Examples 11 to 20 and Comparative Examples 5 to 8.

[0119] Example 21

[0120] 15 parts by weight of the graft copolymer of Example 1, 10 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Asahi Chemical, Korea), and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfa) were uniformly mixed and melt-extruded to obtain an ABS resin composition, which is Example 21.

[0121] Example 22

[0122] 10 parts by weight of the graft copolymer of Example 2, 15 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Asahi Chemical, Korea), and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfa) were uniformly mixed and melt-extruded to obtain an ABS resin composition, which is Example 22.

[0123] Example 23

[0124] 15 parts by weight of the graft copolymer of Example 5, 15 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Asahi Chemical, Korea), 35 parts by weight of SAN resin (KFA-130, Liaoning Jinfa), and 35 parts by weight of SAN resin (PN-128, Zhenjiang Qimei) were uniformly mixed and melt-extruded to obtain an ABS resin composition, which is Example 23.

[0125] Comparative Example 9

[0126] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Asahi Chemical, Korea) and 75 parts by weight of SAN resin (KFA-130, Liaoning Jinfa) were uniformly mixed and melt-extruded to obtain an ABS resin composition, which is Comparative Example 9. Performance test:

[0127] The products prepared in the above examples and comparative examples were subjected to performance tests. The specific test items and test methods are as follows:

[0128] 1. Test method:

[0129] (1) Determination of the conversion rate P of the graft copolymer: 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.

[0130] P 接枝共聚物 =(B·m 总 -m 助剂 -A·m 胶 ) / m 单体

[0131] In the formula, the sum of the feeding masses of all raw materials is m 总 , and 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 / %), and 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.

[0132] (2) Mechanical property test: The ABS resin compositions prepared in the above examples and comparative examples were tested according to the standard of GB / T 12672-2009.

[0133] (3) Test of weight-average molecular weight: The weight-average molecular weight of free SAN was 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;

[0134] Pretreatment of graft copolymer: Take a small amount of the graft copolymer and swell it in acetone, oscillate it at a constant temperature of 55 °C 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 has evaporated completely, 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, then determine 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 tested, and the molecular weight of the graft copolymer is reflected by testing the weight-average molecular weight of free SAN.

[0135] (5) Determination of the content of the functional group-substituted tetralin compound:

[0136] a) Preparation of the test sample, blank solution and external standard sample solution

[0137] Preparation of the test sample: Take a small amount of the graft copolymer 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 it at 85 °C for 48 h, and the resulting extract is filtered through a 0.22 μm filter for standby;

[0138] Preparation of the blank solution: Place the blank filter paper in a Soxhlet extractor, extract it with HPLC-grade methanol at 85 °C for 48 h, and the resulting extract is filtered through a 0.22 μm filter for standby;

[0139] Preparation of the external standard sample solution: Take an appropriate amount of the external standard sample (functional group-substituted tetralin compounds 1-9), and dilute it with HPLC-grade methanol to 10 mg / L;

[0140] b) Content Test of Functional Group-Substituted Tetralin Compounds

[0141] The content of the functional group-substituted tetralin compound was tested by HPLC. The chromatogram was recorded, and the content was calculated according to 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 the 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).

[0142] 2. Test Results

[0143] The test results of each example and comparative example are shown in Tables 1 - 2.

[0144] Table 1 Conversion Rate and Weight-Average Molecular Weight of Each Graft Copolymer

[0145]

[0146]

[0147] Table 2 Mechanical Properties of Each ABS Resin Composition

[0148]

[0149] As can be seen from Table 1, the graft conversion rates of the graft copolymers obtained in Examples 1 - 9 can reach 98.1 - 99.2%, and the weight-average molecular weight of the free SAN is 8.2 - 9.8×10 4 g / mol; as can be seen from Table 2, comparing the test results of Examples 11 - 20 and Comparative Example 6, for the graft copolymer containing the functional group-substituted tetralin compound obtained in the present invention, compared with the graft copolymer prepared solely using the conventional initiator cumene hydroperoxide, the impact strength of the obtained ABS resin composition is better. And from the test results of Examples 11 - 20 and Comparative Example 9 in Table 2, it can be known that the application performance of the graft copolymer containing the functional group-substituted tetralin compound obtained in the present invention is superior to that of the commercially available HR181 high rubber powder with excellent comprehensive performance.

[0150]

[0151] ​Obviously, the above embodiments of the present invention are merely examples for clearly illustrating 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 based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements, improvements, etc. 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. A graft copolymer, characterized in that, The content of the functional group-substituted tetralin shown in the formula I in the graft copolymer is 250 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 carbonyl 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; the carbonyl group includes -CO(CH2) x R; X, y, and z in the functional substituent each independently select any integer value from 0 to 15; Each R independently selects from hydrogen, methyl, amino, cyano, phenyl, hydroxyl, -COOR2, -COR2, carboxyl or aldehyde group; R2 is a straight-chain or branched-chain alkane with 0 to 18 carbon atoms.

2. The graft copolymer according to claim 1, wherein 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 independently selects 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 independently selects from one or more of cyano, -CH(CN)CH3, -CH(-C6H5)CH3, -CH(NH2)CH3, -CH2CN, -COOCH3, -NHCOCH3 or -COOCH2CH3.

3. The graft copolymer 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.

4. The graft copolymer according to any one of claims 1 to 3, characterized in that, The functional group-substituted tetralin compound is: one or more of 5. The graft copolymer according to claim 1, wherein Comprising 100 parts by weight of polyconjugated diene units and 30 to 80 parts by weight of graft monomer units; The polyconjugated diene contains: (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, (meth)acrylic acid C1-C8 alkyl ester, alkylene glycol di(meth)acrylate and vinyl methyl ether; The graft monomer contains: (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 of α-methylstyrene, p-methylstyrene and (meth)acrylic acid C1-C8 alkyl ester; (e): 0 to 50% by weight of monomer B2, and the monomer B2 is selected from acrylonitrile or a mixture of acrylonitrile and at least one of methacrylonitrile, acrylamide, vinyl methyl ether, acid anhydride of unsaturated carboxylic acid and imide of unsaturated carboxylic acid.

6. The graft copolymer according to claim 5, wherein Based on 100 parts by weight of the solid content of the polyconjugated diene, the graft copolymer also 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.

7. The preparation method of the graft copolymer according to any one of claims 1 to 6, characterized in that, Comprising the following steps: The raw material components including polyconjugated diene, graft monomer and auxiliary agent are mixed evenly and subjected to stepwise temperature-raising reaction, and the graft copolymer is obtained through coagulation, dehydration and drying; preferably, the temperature of the first-stage reaction in the stepwise temperature-raising 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 60-60°C, and the reaction time is 50-150 min.

8. An ABS resin composition, characterized in that, The ABS resin composition comprises the following components calculated by weight: Graft copolymer: 15-45 parts; SAN resin: 55-85 parts; Other components: 0-2 parts; The graft copolymer is partially or wholly the graft copolymer containing tetralin substituted by the functional group shown in Formula I according to any one of Claims 1-6.

9. An ABS resin composition as described in claim 8, characterized in that, The content of tetralin substituted by the functional group shown in Formula I in the ABS resin composition is 75-1500 ppm.

10. A method for preparing the ABS resin composition according to claim 8, characterized in that, Comprising the following steps: The raw material components including the graft copolymer and SAN resin are mixed evenly according to a ratio, fed into an extruder, and obtained through melt blending and extrusion granulation.

11. Use of an ABS resin composition according to any one of Claims 8-9 in preparing automotive accessories and home appliance housing materials.

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