Preparation method and application of SAN (styrene-acrylonitrile) resin and ABS (acrylonitrile-butadiene-styrene) resin composition containing SAN resin

Abstract

The invention discloses a preparation method and application of SAN (Styrene Acrylonitrile Butadiene Styrene) resin and an ABS (Acrylonitrile Butadiene Styrene) resin composition containing the SAN resin The SAN resin contains a tetrahydronaphthalene compound substituted by a functional group, and 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 tetrahydronaphthalene compound containing the functional group substituent is used for synthesizing SAN resin, 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 is increased, the cleanliness of the resin is increased, and the service life of the resin is prolonged. And the composition obtained by applying the prepared SAN resin 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 method for preparing a SAN resin and an ABS resin composition including the same, and applications thereof. Background Art

[0002] The homopolymerization and copolymerization of styrene are classical in free radical polymerization, and there is a unique self-initiating mechanism, which involves 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, the excessive addition of the above initiators not only has a limited increase in the conversion rate, but also has a negative impact on the mechanical properties of the material due to a relatively high degree of crosslinking or a relatively 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 addition amount of initiators 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 properties of the material. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above-mentioned defects or deficiencies, and to provide a SAN resin containing a tetrahydronaphthalene compound substituted with a functional group, where 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 SAN resin, 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 polymer is higher, the cleanliness is higher, and the mechanical properties of the ABS resin composition obtained from the prepared SAN resin are better.

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

[0006] A SAN resin, wherein the content of the tetrahydronaphthalene substituted with the functional group shown in Formula Ⅰ in the SAN resin is 200 to 2000 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 each independently select any integer value from 0 to 15; preferably select any integer value from 0 to 3;

[0011] 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, preferably R2 is a straight-chain or branched-chain alkane with 0 to 3 or 10 to 14 carbon atoms.

[0012] The content of the functional group-substituted tetralin shown in Formula I in the SAN resin in the present invention is 200 to 2000 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, 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.

[0013] Further, each of A to D is 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] Each of E to H is 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 a functional group is:[[]]

[0019]

[0020] One or more of the above.

[0021] The present invention also discloses a SAN resin, which is a copolymer comprising an aromatic vinyl monomer and an alkenyl nitrile monomer.

[0022] Further, the SAN resin comprises the following monomer units:

[0023] (a): 65 to 90% 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; preferably, 70 to 80 parts by weight of at least one aromatic vinyl monomer B1;

[0024] Further, the aromatic vinyl monomer B1 is at least one of styrene, methyl acrylate or methyl methacrylate.

[0025] (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, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids; preferably, 20 to 30 parts by weight of at least one monomer B2;

[0026] Further, the monomer B2 is acrylonitrile and / or acrylamide.

[0027] (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.

[0028] 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, diacetone acrylamide, divinyltetramethoxydisilane or 1,4-bis(vinyldimethylsilyl)benzene.

[0029] Further, the polyfunctional crosslinking monomer B3 is at least one of divinylbenzene, allyl acrylate, allyl methacrylate or divinyltetramethoxydisilane.

[0030] 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.

[0031] Further, the copolymerization is completed by emulsion polymerization.

[0032] In some specific embodiments, the SAN resin further comprises 0.01-0.5% by weight of a molecular weight regulator; 0-0.05% by weight of an initiator.

[0033] In the present invention, the other initiators include azo initiators or peroxide initiators.

[0034] Specifically, the azo initiator is azobisisobutyronitrile.

[0035] The peroxide initiator is benzoyl peroxide and / or cumene hydroperoxide.

[0036] In the present invention, the molecular weight regulators include one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, tetradecyl mercaptan, tridecyl mercaptan, undecyl mercaptan, and decyl mercaptan.

[0037] In some specific embodiments, 5-25 parts of a solvent are further included in the preparation process of the SAN resin.

[0038] In the present invention, the solvent can be selected with reference to the prior art, such as toluene, ethylbenzene, propylbenzene, acetonitrile, ethylacetonitrile, and / or propylacetonitrile.

[0039] The present invention also provides a method for preparing a SAN resin, comprising the following steps:

[0040] Mix the raw material components and carry out a polymerization reaction at 80-180°C, and remove volatiles to obtain the SAN resin.

[0041] The raw material components include aromatic vinyl monomers, vinyl cyanide monomers, molecular weight regulators, initiators, and solvents.

[0042] The polymerization reaction includes solution polymerization, bulk polymerization, or suspension polymerization.

[0043] In some specific embodiments, the polymerization reaction time is 1-3 hours.

[0044] The present invention also provides an ABS resin composition, which comprises the following components calculated by weight:

[0045] Graft copolymer 15-45 parts;

[0046] SAN resin 55-85 parts;

[0047] Other components 0-2 parts.

[0048] Further, part or all of the SAN resin is a SAN resin of tetralin substituted by the functional group shown in Formula I.

[0049] Further, the mass ratio of the SAN resin of tetralin substituted by the functional group shown in Formula I in the ABS resin composition to the SAN resin can be 1 to 100%. For example, 2%, 5%, 10%, 25%, 50%, 75%, 95%, or the range between any of the above values.

[0050] Further, the content of tetralin substituted by the functional group shown in Formula I in the ABS resin composition is 150 to 1500 ppm.

[0051] The content of tetralin substituted by the functional group shown in Formula I in the ABS resin composition is 150 to 1500 ppm. For example, but not limited to, 150 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm, 200 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 the range between any of the above values.

[0052] 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 bactericide or a foaming agent.

[0053] 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.

[0054] Specifically, the pigment includes, but is not limited to, one or more of titanium dioxide, phthalocyanine, ultramarine, iron oxide or carbon black.

[0055] Specifically, the stabilizer includes, but is not limited to, one or more of light stabilizer 770, light stabilizer 944, salicylate, benzotriazole or benzophenone.

[0056] Specifically, the mold 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.

[0057] 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.

[0058] 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].

[0059] Specifically, the phosphite antioxidant is 2,4-di-tert-butylphenol and / or bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0060] Specifically, the thioester antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol tetrakis(3-laurylthiopropionate).

[0061] 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.

[0062] The present invention also provides a method for preparing an ABS resin composition, comprising the following steps:

[0063] 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.

[0064] The present invention also provides the application of the ABS resin composition in the preparation of automotive accessories and household appliance housing materials.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] In the present invention, the SAN resin 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 SAN resin, it can initiate the polymerization reaction, reduce the dosage of the traditional initiator, improve the molecular weight while achieving a comparable conversion rate, increase the resin cleanliness, and the mechanical properties of the composition obtained by applying the prepared SAN resin are better; because the SAN resin of the present invention has a higher molecular weight, the ABS resin composition prepared therefrom has higher mechanical properties. Specific embodiments

[0067] 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.

[0068] Raw materials used in each example and comparative example:

[0069] Styrene: 99%, 10 - 15 ppm TBC, purchased from Macklin;

[0070] Acrylonitrile: 99%, 10 - 15 ppm MEHQ, purchased from Macklin;

[0071] Functionally substituted tetrahydronaphthalene compounds:

[0072] Functionally substituted tetrahydronaphthalene compound 1: CAS No.: 57964 - 39 - 3, purchased from CATO;

[0073] Functionally substituted tetrahydronaphthalene compound 2: CAS No.: 26681 - 79 - 8, purchased from Wako;

[0074] Functionally substituted tetrahydronaphthalene compound 3: CAS No.: 91562 - 48 - 0, purchased from Apinno;

[0075] Functionally substituted tetrahydronaphthalene compound 4: CAS No.: 2510 - 03 - 4, purchased from Sigma - aldrich;

[0076] Functionally substituted tetrahydronaphthalene compound 5: CAS No.: 57964 - 40 - 6, purchased from CATO;

[0077] Functionally substituted tetrahydronaphthalene compound 6: CAS No.: 59604 - 96 - 5, purchased from Macklin;

[0078] Functionally substituted tetrahydronaphthalene compound 7: CAS No.: 948006 - 26 - 6, purchased from Yuanye;

[0079] Functionally substituted tetrahydronaphthalene compound 8: CAS No.: 218903 - 61 - 8, purchased from Leyan;

[0080] Functionally substituted tetrahydronaphthalene compound 9: CAS No.: 1042797-88-5, purchased from Leyan;

[0081] Methyl-substituted tetrahydronaphthalene compound: CAS No.: 119-64-2, purchased from Aladdin;

[0082] Initiator:

[0083] Cumene hydroperoxide, commercially available;

[0084] Azobisisobutyronitrile, commercially available;

[0085] 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 are all the same commercially available products;

[0086] Examples 1-9

[0087] In Examples 1-9, the preparation method of the SAN resin is as follows:

[0088] Add 25 parts by weight of acrylonitrile and 75 parts by weight of styrene to 15 parts by weight of ethylbenzene, and add 0.3 part by weight of molecular weight regulator, 0.1 part by weight of the tetrahydronaphthalene compound substituted with the functional group shown in Formula I, and 0.01 part by weight of azobisisobutyl nitrile into a sealed reaction kettle after nitrogen replacement. Heat up to 135 °C to start the polymerization reaction. After reacting for 2 hours, transfer it to a devolatilization kettle for devolatilization to obtain the SAN resin; Examples 11-19 respectively use tetrahydronaphthalene compounds 1-substituted with functional groups to tetrahydronaphthalene compounds 9-substituted with functional groups.

[0089] Example 10

[0090] The preparation method is the same as that of Example 1, except that 0.11 part by weight of the tetrahydronaphthalene compound substituted with functional group 1 is used in its entirety.

[0091] Comparative Example 1

[0092] The preparation method is the same as that of Example 1, except that in Comparative Example 1, the methyl-substituted tetrahydronaphthalene compound is selected to replace the tetrahydronaphthalene compound substituted with functional group 1 in an equal amount.

[0093] Comparative Example 2

[0094] The preparation method is the same as that of Example 1, except that in Comparative Example 2, 0.11 part by weight of azobisisobutyl nitrile is used in its entirety.

[0095] Comparative Example 3

[0096] The preparation method is the same as that of Example 1, except that in Comparative Example 3, 0.5 part by weight of the tetrahydronaphthalene compound substituted with functional group 1 and 0.01 part by weight of azobisisobutyl nitrile are used.

[0097] Comparative Example 4

[0098] The preparation method was the same as that of Example 1, except that in Comparative Example 4, 0.02 parts by weight of the functional group-substituted tetrahydronaphthalene compound 1 and 0.01 parts by weight of azobisisobutyronitrile were used.

[0099] Examples 11 to 20 and Comparative Examples 5 to 8

[0100] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Petrochemical, South Korea) and 75 parts by weight of the SAN resin prepared in Examples 1 to 10 and Comparative Examples 1 to 4 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 designated as Examples 11 to 20 and Comparative Examples 5 to 8, respectively.

[0101] Example 21

[0102] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Petrochemical, South Korea), 50 parts by weight of the SAN resin prepared in Example 1, and 25 parts by weight of a SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly, and melt-extruded to obtain an ABS resin composition, which was Example 21.

[0103] Example 22

[0104] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Petrochemical, South Korea), 40 parts by weight of the SAN resin prepared in Example 2, and 35 parts by weight of a SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly, and melt-extruded to obtain an ABS resin composition, which was Example 22.

[0105] Example 23

[0106] 15 parts by weight of graft copolymer A (ABS high rubber powder, HR-181, Kumho Petrochemical, South Korea), 15 parts by weight of graft copolymer B (ABS high rubber powder, MAG50, Ineos Styrolution, Thailand), 30 parts by weight of the SAN resin prepared in Example 5, and 40 parts by weight of a SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly, and melt-extruded to obtain an ABS resin composition, which was Example 23.

[0107] Comparative Example 9

[0108] 25 parts by weight of a graft copolymer (ABS high rubber powder, HR-181, Kumho Petrochemical, South Korea) and 75 parts by weight of a SAN resin (KFA-130, Liaoning Jinfa) were mixed evenly, and melt-extruded to obtain an ABS resin composition, which was Comparative Example 9. Performance test:

[0109] 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:

[0110] 1. Test method:

[0111] (1) The method for determining the monomer conversion rate of SAN resin polymerization is as follows:

[0112] P SAN =(m 聚合物 -m 助剂 ) / m 单体

[0113] In the formula, the sum of the masses of the monomers is m 单体 , the mass of the obtained SAN resin is 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.

[0114] (2) Mechanical property test: The ABS resin compositions prepared in the above examples and comparative examples were tested according to the standard of GB / T12672-2009.

[0115] (3) Test of weight-average molecular weight: The weight-average molecular weight of SAN resin 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;

[0116] Pretreatment of SAN resin: Take a small amount of SAN resin and dissolve it in tetrahydrofuran for 12 h, and filter it into the injection bottle through a microporous filter;

[0117] (4) Determination of the content of functional group-substituted tetralin compounds:

[0118] a) Preparation of test sample, blank solution and external standard sample solution

[0119] Preparation of test sample: Take a small amount of SAN resin or ABS resin composition and immerse it in liquid nitrogen for 2 min, transfer it to a mechanical grinder and grind it into 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 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 0.22 μm and reserved for use;

[0120] 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 0.22 μm and reserved for use;

[0121] Preparation of external standard sample solution: Take an appropriate amount of external standard samples (functionally substituted tetrahydronaphthalene compounds 1-9), and dilute them with HPLC-grade methanol to 10 mg / L;

[0122] b) Content test of functionally substituted tetrahydronaphthalene compounds

[0123] The content of functionally substituted tetrahydronaphthalene compounds was tested by HPLC. The chromatogram was recorded, and the content was calculated by the external standard method; Detection equipment: Waters ACQUITY Arc LC; Detector: Waters 2998 photodiode array detector, monitoring range: 190-400 nm; Chromatographic column model: Multospher "120RP 18HP 5μm, 250×2mm, Mobile phase A: 0.01% formic acid aqueous solution by volume, Mobile phase B: methanol, Injection volume 10 μL; Column oven temperature: 50 °C; Mobile phase flow rate: 0.2 mL / min; Separation gradient: Mobile phase B increases from 40% to 100% within 40 minutes and is maintained for 10 minutes, and is 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).

[0124] 2. Test results

[0125] The test results of each example and comparative example are shown in Tables 1-2.

[0126] Table 1 Conversion rate and weight-average molecular weight of each SAN resin

[0127]

[0128]

[0129] Table 2 Mechanical properties of each ABS resin composition

[0130]

[0131]

[0132] From the test results of Examples 1-9 and Comparative Example 2 in Table 1, it can be seen that the polymerization monomer conversion rate of SAN resin containing functionally substituted tetrahydronaphthalene compounds is comparable or even higher, and the molecular weight is higher. The monomer conversion rate of the SAN resin obtained in Examples 1-9 can reach 47.9-49.2%, and the weight-average molecular weight is 8.5-9.5×10 4g / mol. From the test results of Examples 11 to 19 and Comparative Example 6, it can be seen that the notched Izod impact strength of the ABS resin composition corresponding to the SAN resin containing the tetrahydronaphthalene compound substituted with a functional group is higher. From the test results of Examples 11 to 19 and Comparative Example 9 in Table 2, it can be seen that the performance of the SAN resin containing the tetrahydronaphthalene compound substituted with a functional group is superior to that of the commercially available KFA-130 resin with excellent comprehensive performance.

[0133] Obviously, the above-mentioned 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 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 in the protection scope of the claims of the present invention.

Claims

1. A SAN resin, characterized in that, The content of the functional group-substituted tetralin shown in Formula I in the SAN resin is 200 to 2000 ppm; Among them, at least one of A to H is a functional substituent, and the functional substituents include 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 substituents are 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 with 0 to 18 carbon atoms.

2. The SAN resin 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 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.

3. The SAN resin according to claim 1, wherein 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 SAN resin 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 SAN resin according to any one of claims 1 to 4, characterized in that, Including the following monomer units: (a): 65 to 90% by weight of at least one aromatic vinyl monomer B1, and 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, and the monomer B2 is selected from acrylonitrile or a mixture of acrylonitrile and at least one other monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, acid anhydride of unsaturated carboxylic acid and imide of unsaturated carboxylic acid; (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.

6. The SAN resin according to claim 5, wherein It also contains 0.01 to 0.5% by weight of a molecular weight regulator; 0 to 0.05% by weight of an initiator.

7. A method for preparing the SAN resin according to any one of claims 1 to 6, characterized in that, Including 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 a SAN resin.

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

9. An ABS resin composition according to claim 8, characterized in that, The content of the functional group-substituted tetralin shown in Formula I in the ABS resin composition is 150 to 1500 ppm.

10. A method for preparing the ABS resin composition according to claim 8, characterized in that, Including 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.

11. Use of the ABS resin composition according to any one of claims 8 to 9 in the preparation of automotive accessories and home appliance housing materials.

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