Styrene-butadiene impact-resistant transparent resin with functionalized chain end containing silicon group and preparation method of styrene-butadiene impact-resistant transparent resin

Abstract

The invention belongs to the field of synthesis and functionalization of styrene-butadiene anti-impact transparent resin, and aims to prepare the styrene-butadiene anti-impact transparent resin with a chain end containing a silicon group functionalization in order to solve the problems that the structure and the performance of styrene-butadiene resin cannot be accurately regulated and controlled and multifunctional application is insufficient in the prior art. The styrene-butadiene anti-impact transparent resin is a segmented copolymer of styrene, butadiene, isoprene and a silicon group-containing functionalized 1, 1-diphenylethylene derivative, and the content of the silicon group-containing functionalized 1, 1-diphenylethylene derivative is 0.2%-2%. The silicon group-containing functionalized 1, 1-diphenylethylene derivative is introduced into the chain end of the butylbenzene anti-impact transparent resin, the butylbenzene anti-impact transparent resin with the chain end containing the silicon group functionalization is constructed, the transparency range is 80%-95%, the haze range is 3%-30%, and the impact strength range is 0.5-30 kJ / m < 2 >. The optical property and the mechanical property of the styrene-butadiene resin are remarkably improved, and the styrene-butadiene resin has a good industrial prospect.

Description

Technical Field

[0001] The invention belongs to the field of synthesis and functionalization of styrene-butadiene impact-resistant transparent resins, and particularly relates to a type of styrene-butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends and a preparation method thereof. Background Art

[0002] Styrene-butadiene impact-resistant transparent resin, abbreviated as K resin, is a styrene-butadiene block copolymer with a high styrene content (50wt%-85wt%). It not only exhibits high transparency and good impact resistance, but also boasts physiological safety and excellent recyclability, making it one of the most widely used polymers. Styrene-butadiene impact-resistant transparent resin has a vast market and development potential, playing an important role in packaging, plastics, medical devices, toys, furniture, instrumentation, and other fields. Furthermore, styrene-butadiene resin can be blended and modified with a variety of plastics, giving K resin significant potential in the engineering plastics processing sector.

[0003] Currently, the synthesis of styrene-butadiene resins is primarily based on anionic polymerization, using styrene and butadiene as comonomers and alkyl lithium as initiators. From initially synthesizing linear structures by manipulating microstructure and composition, to synthesizing diverse products with varying sequences and topologies, and finally to multifunctional modifications tailored to specific needs, styrene-butadiene resins have undergone a long and fruitful development process. Countries such as the United States, Germany, and Japan have pioneered the development of various styrene-butadiene resin grades to meet diverse product needs, including KR04, KR10, and KK38 from Philips (USA); 644D, 693D, 3G33, and 3G35 from BASF (Germany); and 825, 830, and 885S from Asahi Kasei (Japan). With the continuous development of my country's chemical industry, Maoming Zhonghe Plastics has also launched a variety of styrene-butadiene resin grades, such as the SL838 high-impact modified grade, the SL805 grade for extrusion and calendered sheet, and the 8300 high-modulus, high-hardness injection molding grade.

[0004] The structure and performance of styrene-butadiene resin are inseparable. For example, the mass fraction of styrene can be adjusted according to product requirements, and the sequence structure mainly includes linear gradient blocks, linear random blocks, linear pure blocks, etc. In addition, factors such as molecular weight and microstructure also affect the performance of styrene-butadiene resin. In summary, there is still little research on the multifunctional modification of styrene-butadiene resin, and its multifunctional application needs to be broken through. In addition, there is a lack of systematic "structure-activity" relationship research. How to further accurately control the structure of styrene-butadiene resin and improve its performance is a technical problem to be solved in the present invention. Summary of the Invention

[0005] In response to the problems of the existing technology such as the inability to precisely control the structure and performance of styrene-butadiene resins and their insufficient multifunctional applications, the present invention introduces a silicon-functionalized 1,1-diphenylethylene DPE derivative (Si-DPE) into the chain end of styrene-butadiene impact-resistant transparent resins, constructing a class of styrene-butadiene impact-resistant transparent resins with silicon-functionalized chain ends, which significantly improves the optical and mechanical properties of styrene-butadiene resins and has good industrial prospects.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a class of styrene-butadiene impact-resistant transparent resins (Si-SIBCs) functionalized with silicon groups at the chain ends, wherein the styrene-butadiene impact-resistant transparent resins functionalized with silicon groups at the chain ends are block copolymers of styrene (St), butadiene (Bd), isoprene (Ip), and 1,1-diphenylethylene derivatives (Si-DPE) functionalized with silicon groups;

[0008] Based on the mass of the chain-end silicon-functionalized styrene-butadiene impact-resistant transparent resin (Si-SIBC) copolymer as 100%, the styrene (St) content is 45% to 90%, preferably in the range of 65% to 85%, the isoprene (Ip) content is 0 to 15%, preferably in the range of 8 to 12%, the content of the silicon-functionalized 1,1-diphenylethylene derivative is 0.2% to 2%, and the rest is butadiene (Bd).

[0009] Furthermore, the number average molecular weight M of the chain end silicon-containing group functionalized styrene-butadiene impact-resistant transparent resin is n The molecular weight distribution index (PDI) is in the range of 100,000 to 500,000, preferably 100,000 to 300,000, and the molecular weight distribution index (PDI) is in the range of 1.02-1.50.

[0010] Furthermore, the silicon-containing functionalized 1,1-diphenylethylene derivative is selected from diphenylethylene derivatives containing siloxy groups, silicon hydride groups and silicon hydride groups; the siloxy groups, silicon hydride groups and silicon hydride groups are connected to the para position, meta position or ortho position of the phenyl group in the 1,1-diphenylethylene derivative; preferably, the para position contains silicon hydride groups and silicon hydride groups.

[0011] In a second aspect, the present invention provides a method for preparing a type of styrene-butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain end, comprising the following steps:

[0012] S1. Under nitrogen or argon protection, add a measured amount of a non-polar solvent, a polarity regulator, and a silicon-containing functionalized 1,1-diphenylethylene derivative monomer into a polymerization reactor, adjust to a set temperature, add an alkyl lithium initiator according to the measured amount, the initiation temperature range is 10-90°C, the initiation time is 3-10 hours, and then add monomers styrene (St), butadiene (Bd), and isoprene (Ip) in a set order, the reaction temperature is controlled at 30-110°C, and the reaction time is 1-10 hours;

[0013] S2, preparing a butadiene-styrene impact-resistant transparent resin functionalized with a silicon group at the chain end, specifically selected from one of the following three operations:

[0014] S21, adding a terminator and an antioxidant, stirring evenly and then discharging to prepare a styrene-butadiene impact-resistant transparent resin with a chain initiator end functionalized with a silicon group;

[0015] S22. After the monomer reaction is completed, add a silicon-containing functionalized 1,1-diphenylethylene derivative monomer to the polymerization reactor for end-capping, the reaction temperature is 50-110° C., the reaction is continued for 1-3 hours, a terminator and an antioxidant are added, and the mixture is stirred evenly before discharging to prepare a butadiene-styrene impact-resistant transparent resin with silicon-containing functionalized chain initiation ends and chain termination ends;

[0016] S23. Add a linear coupling agent to the polymerization reactor, continue the reaction for 0.5 to 5 hours, control the reaction temperature at 30-110°C, add a terminator and an antioxidant, stir evenly and then discharge the material to obtain a butadiene-styrene impact-resistant transparent resin functionalized with silicon groups at the chain ends, wherein both the chain initiation end and the chain termination end have 1,1-diphenylethylene derivative groups functionalized with silicon groups.

[0017] On the other hand, the present invention provides a method for preparing a type of styrene-butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain end, comprising the following steps:

[0018] Under nitrogen or argon protection, a measured amount of a non-polar solvent and a polarity regulator are added to a polymerization reactor, the temperature is adjusted to a set temperature, an alkyl lithium initiator is added according to the measured amount, the initiation temperature range is 10-90° C., and the initiation time is 3-10 hours; then, reaction monomers styrene (St), butadiene (Bd), and isoprene (Ip) are added, the reaction temperature is controlled at 30-110° C., and the reaction time is 1-10 hours; then, a linear coupling agent is added to the polymerization reactor, the reaction is continued for 0.5-5 hours, the reaction temperature is controlled at 30-110° C., a silicon-containing group functionalized 1,1-diphenylethylene derivative monomer is added to the polymerization reactor for end-capping, the reaction temperature is 50-110° C., the reaction is continued for 1-3 hours, a terminator and an antioxidant are added, stirred evenly, and then the material is discharged to obtain the butadiene-styrene impact-resistant transparent resin with silicon-containing group functionalized on the chain end; wherein the chain terminator has a silicon-containing group functionalized 1,1-diphenylethylene derivative group.

[0019] Furthermore, the molar ratio of the total amount of the silicon-containing functionalized 1,1-diphenylethylene derivative added in each step to the alkyl lithium initiator is (1-5):1.

[0020] Furthermore, the molar ratio of the polarity regulator to the alkyl lithium initiator is (0.5-5):1;

[0021] Furthermore, the mass ratio of styrene (St), butadiene (Bd), and isoprene (Ip) is (0.8-1.6):1:(0-0.3);

[0022] Furthermore, the molar ratio of the linear coupling agent to the alkyl lithium initiator is (1-3):1; the molar ratio of the terminator to the alkyl lithium initiator is (1-10):1.

[0023] Furthermore, the mass fraction of the three reactive monomers, styrene (St), butadiene (Bd), and isoprene (Ip), in the solution is 5-20%.

[0024] Furthermore, the mass ratio of the antioxidant to the three reaction monomers of styrene (St), butadiene (Bd), and isoprene (Ip) is 1: (1000-10000), and the mass ratio of the antioxidant to the three reaction monomers of styrene (St), butadiene (Bd), and isoprene (Ip) is 1: (1000-10000).

[0025] Furthermore, the silicon-containing functionalized 1,1-diphenylethylene derivative is selected from diphenylethylene derivatives containing siloxy groups, silicon hydride groups and siloxy groups / silicon hydride groups.

[0026] Furthermore, the non-polar solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, methylcyclohexane, mixed aromatic hydrocarbons (such as mixed xylenes), mixed aliphatic hydrocarbons (such as raffinate oil), preferably hexane, cyclohexane, pentane, methylcyclohexane and mixed solvents thereof;

[0027] Furthermore, the mass fraction of the monomer in the solvent is preferably in the range of 8 to 15%.

[0028] Furthermore, the alkyl lithium initiator is n-butyl lithium and sec-butyl lithium.

[0029] Furthermore, the polarity regulator is tetrahydrofuran, 2,2-bis(2-tetrahydrofuranyl)propane, 2,2-bis(5-methyl-2-tetrahydrofuranyl)propane, ethyltetrahydrofuranyl ether, tetramethylethylenediamine, and diethylene glycol diethyl ether; whether to use polar additives is determined based on the designed microstructure and sequence structure.

[0030] Furthermore, the oxidant is selected from 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), β-(3.5-di-tert-butyl, 4-hydroxyphenyl) propionate, 2,6-di-tert-butylphenol, preferably N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, and N-isopropyl-N'-phenyl-p-phenylenediamine.

[0031] Furthermore, the linear coupling agent is selected from R(CH3)2Cl2 or 1,2-dichloroethane or 1,2-dibromoethane, R is a metal atom selected from silicon (Si), tin (Sn), lead (Pb), titanium (Ti), germanium (Ge) metal elements, preferably dichlorodimethylsilane.

[0032] Beneficial effects

[0033] The styrene butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain end prepared by the present invention can react with various functional groups such as olefins, alkynyls, and hydroxyls, thereby enriching the categories of styrene butadiene impact-resistant transparent resins and facilitating their further functionalization modification; the problems of easy oxidation and coloration existing in general styrene butadiene impact-resistant transparent resins functionalized with nitrogen-containing groups are solved, and the optical properties of the material are improved; the introduction of isoprene Ip into the styrene butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain end improves the elongation at break and the melt flow rate of the styrene butadiene impact-resistant transparent resin; and the functionalization modification with a silicon-containing group improves the impact performance of the styrene butadiene impact-resistant transparent resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 GPC curves of non-functionalized styrene butadiene impact-resistant transparent resin and styrene butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends;

[0035] Figure 2 The hydrogen nuclear magnetic resonance spectra of the non-functionalized styrene butadiene impact-resistant transparent resin and the styrene butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends;

[0036] Figure 3 The following are actual pictures of samples of non-functionalized styrene butadiene impact-resistant transparent resin and styrene butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends;

[0037] Figure 4 These are the impact cross-sectional morphologies of non-functionalized styrene butadiene impact-resistant transparent resin and styrene butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends. DETAILED DESCRIPTION

[0038] The present invention will be described in detail below in conjunction with specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific embodiments and examples are for illustrating the present invention, rather than for limiting the present invention.

[0039] Throughout this specification, unless otherwise specified, the terms used herein should be understood as having the same meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of any conflict, the present specification shall take precedence.

[0040] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0041] (1) Injection molding of styrene-butadiene resin

[0042] The injection molding machine is a Haake minijet pro produced by Thermo Fisher Scientific. The barrel temperature is 160-170°C, the mold temperature is 40°C, the pressure is 300 bar or 350 bar, the injection holding time and the mold holding time are both 10 seconds, and the injection molded specimens are left to stand at room temperature for 24 hours to fully release the internal stress before use.

[0043] (2) Melt flow rate test

[0044] The test instrument is an MFI-1211 melt flow rate tester manufactured by Jinjian Testing Instrument Co., Ltd. The test follows ISO 1133 standards, with a load of 2.16 kg, an automatic cutting interval of 10 or 20 seconds, and ten cuts. During the test, the instrument barrel is heated to 190°C and then held constant. The resin sample is placed in the barrel and allowed to stand for 3 minutes until it melts. The sample is then evenly extruded using the load. Samples are collected and weighed after each cut, and the average result is calculated.

[0045] (3) Shore hardness test

[0046] The test instrument used was an LX-DY digital Shore hardness tester manufactured by Longrun Technology Co., Ltd. The specimen dimensions were identical to those used in the bending test. The test was conducted in accordance with ISO 868. The specimen was placed on a solid surface. The indenter of the durometer was pressed vertically into the specimen surface, ensuring full contact between the indenter and the specimen. A pressure of 1 kg was applied. The hardness value was read 15 seconds after the indenter had been in full contact with the specimen. Five tests were performed on each sample, and the results were averaged.

[0047] (4) Vicat softening point test

[0048] The test instrument was a VTM1600 microcomputer-controlled thermal deformation Vicat softening tester manufactured by Sansi Zongheng Technology Co., Ltd. The specimen dimensions were identical to those used in the bending tests. The test was conducted in accordance with ISO 306. The sample was placed on the test bench, and the indenter was positioned to contact the sample surface. The test program was started and the sample was heated according to the set conditions (heating rate of 120°C / h, state-controlled temperature of 50°C), while the indenter was controlled to move downward at a constant rate. The temperature at which the indenter penetrated the sample surface to the predetermined depth was recorded. Five tests were performed for each sample, and the results were averaged.

[0049] (5) Optical performance test

[0050] The test instrument was a YH1200 haze meter manufactured by Tri-En Technology Co., Ltd. The test was conducted according to ASTM D1003, and the instrument calibration was performed according to JJF 1303-2011. The illumination source was a 400-700nm LED light source. During testing, the sample surface was ensured to be flat, free of foreign matter, scratches, oil stains, dust, and visible defects and particles. The test specimens were injection molded and measured (30 ± 2) mm × (30 ± 2) mm × (1 ± 0.1) mm. Five tests were performed on each sample, and the results were averaged.

[0051] (6) Mechanical properties test

[0052] The tensile and flexural properties testing instrument was a 5567A materials testing machine produced by Instron. The tensile test was conducted in accordance with ISO 527, with a tensile rate of 5 mm / min, an effective distance of 25 mm, and a spline shape and size of the ISO 527-2-5A standard dumbbell spline. The tensile strength, elongation at break, and Young's modulus of the corresponding specimens were recorded. Five experiments were performed for each specimen, and the median value was used for the final result. The flexural test was conducted in accordance with ISO 178, with a bending rate of 2 mm / min, a span of 64 mm, and a spline size of (80 ± 2) mm × (10 ± 2) mm × (4 ± 2) mm. The flexural modulus and maximum flexural stress of the corresponding specimens were recorded. Five experiments were performed for each specimen, and the median value was used for the final result. Izod notched impact testing was performed using a GT-7045-ALN impact tester manufactured by Gotech. The notches were created using a GT-7015-A3 specimen flattening tester manufactured by Gotech. The notch depth was (2 ± 0.2) mm. Testing was conducted according to ISO 180 / A, with a 5.5J pendulum, a 62mm span, and a pendulum angle of (150 ± 0.2) mm. The specimen dimensions were identical to those used in the bending tests. The notched impact strength of each specimen was recorded. Five tests were performed for each sample, and the results were averaged.

[0053] (7) H NMR spectroscopy ( 1 H-NMR)

[0054] The test instrument is a Varian DLG400 MHz NMR spectrometer manufactured by Varian, with tetramethylsilane (δ = 0 ppm) as the internal standard. An appropriate amount of the sample to be tested (5-10 mg) is dissolved in deuterated chloroform and tested at room temperature. This test method is used to determine the molecular structure of monomers and polymers.

[0055] (8) Gas chromatography / triple quadrupole mass spectrometry (GC-MS)

[0056] The test instrument is an Agilent 7000B Triple Quadrupole gas chromatograph / triple quadrupole mass spectrometer. This test method is used for the structural analysis of monomers.

[0057] (9) Gel permeation chromatography (GPC)

[0058] The test instrument is a Waters 1515 chromatography system (equipped with HT4 and HT5 separation columns and a 2414 differential detector) manufactured by Waters. THF is used as the mobile phase at a flow rate of 1.0 ml / min, the column temperature is 35°C, and the instrument calibration standard is PS. This test method is used to determine the molecular weight and distribution of polymers.

[0059] (10) Differential Scanning Calorimetry (DSC)

[0060] The test instrument is TA Q2000 produced by TA. The test is carried out under nitrogen protection, with a heating and cooling rate of 10℃ / min and a test temperature range of -100-160℃. This test method is used to determine the T g .

[0061] (11) Scanning electron microscopy (SEM)

[0062] The test instrument used was a SEM5000 scanning electron microscope (SEM) manufactured by Guoyi Quantum, with an accelerating voltage range of 20V-30kV and a resolution of 1.0nm or less. This test method was used to observe the morphology of the impact cross-section of the spline. Before testing, a conductive film was applied to the notched surface of the spline using a Quorum Q150T coating system to improve SEM imaging quality.

[0063] The present invention is further described below through specific embodiments.

[0064] Example 1

[0065] Step S1, synthesizing monomer DPE-SiH:

[0066] 1.1) Under nitrogen, dry methyltriphenylphosphonium bromide (10 g, 0.021 mol) and potassium tert-butoxide powder (2.14 g, 0.019 mol) were dissolved in 50 ml of dry THF and stirred at 0°C until the solution turned yellow. A THF solution (20 ml) of 4-bromobenzoylbenzene (3.40 g, 0.013 mol) was then added dropwise to the solution. The reaction was stirred at -20°C. After completion of the reaction, the solution exhibited an orange-red color. The solution was quenched with 10 ml of deionized water, which immediately faded to gray with the formation of an off-white precipitate. The solution was filtered to remove salt and the filtrate was extracted with ethyl acetate and saturated sodium chloride solution to obtain a light orange organic phase. Anhydrous magnesium sulfate was added to the organic phase, stirred, and the filtrate was collected. The solvent was removed by vacuum rotary evaporation to obtain a crude product, which was purified by column chromatography (n-hexane as the developing solvent) to obtain a colorless, transparent liquid, DPE-Br.

[0067] 1.2) Add DPE-Br (12.85 g, 0.049 mol) and 80 ml of dry THF to Vial I, seal the apparatus, and stir until ready for use. Add magnesium turnings and iodine granules to Vial II. Add a small amount of the liquid from Vial I dropwise to Vial II. Heat the system to initiate the reaction, then add the remaining liquid dropwise to the system. Heat and stir for 2 hours, then cool until ready for use. Under nitrogen, transfer the supernatant from Vial II to Vial III and add dimethylchlorosilane (6.90 g, 0.074 mol) dropwise. Stir the reaction at room temperature for 12 hours. After completion of the reaction, quench the reaction with 10 ml of deionized water and pour the system into a large amount of n-hexane until a white precipitate forms. Collect the supernatant and remove the solvent by vacuum rotary evaporation to obtain the crude product. Purify the crude product by column chromatography (n-hexane as the developing solvent) to obtain a transparent, viscous liquid. Further purification by vacuum distillation yields pure DPE-SiH.

[0068] Step S2, synthesizing a styrene-butadiene impact-resistant transparent resin functionalized with a silicon group at the chain initiation end:

[0069] Under nitrogen or argon protection, 1000g toluene, 0.1g tetrahydrofuran and 0.1g DPE-SiH monomer were added to the polymerization reactor, the temperature was adjusted to 10°C, 1ml alkyl lithium initiator was added and the reaction was initiated for 3h, and monomers St (50g), Bd (10g), and Ip (5g) were added in sequence. The system was reacted at 30°C for 1h, and finally 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (0.1g) was added. After stirring evenly, the product was discharged. The number average molecular weight of the product is M n The molecular weight distribution index PDI is 1.02, the transparency is 80%, the haze is 10%, and the impact strength is 10kJ / m 2 .

[0070] Example 2

[0071] Step S1, synthesizing monomer DPE-SiH:

[0072] 1.1) Under nitrogen, dry methyltriphenylphosphonium bromide (10 g, 0.021 mol) and potassium tert-butoxide powder (2.14 g, 0.019 mol) were dissolved in 50 ml of dry THF and stirred at 0°C until the solution turned yellow. A THF solution (20 ml) of 4-bromobenzoylbenzene (3.40 g, 0.013 mol) was then added dropwise to the solution. The reaction was stirred at -20°C. After completion of the reaction, the solution exhibited an orange-red color. The solution was quenched with 10 ml of deionized water, which immediately faded to gray with the formation of an off-white precipitate. The solution was filtered to remove salt and the filtrate was extracted with ethyl acetate and saturated sodium chloride solution to obtain a light orange organic phase. Anhydrous magnesium sulfate was added to the organic phase, stirred, and the filtrate was collected. The solvent was removed by vacuum rotary evaporation to obtain a crude product, which was purified by column chromatography (n-hexane as the developing solvent) to obtain a colorless, transparent liquid, DPE-Br.

[0073] 1.2) Add DPE-Br (12.85 g, 0.049 mol) and 80 ml of dry THF to Vial I, seal the apparatus, and stir until ready for use. Add magnesium turnings and iodine granules to Vial II. Add a small amount of the liquid from Vial I dropwise to Vial II. Heat the system to initiate the reaction, then add the remaining liquid dropwise to the system. Heat and stir for 2 hours, then cool until ready for use. Under nitrogen, transfer the supernatant from Vial II to Vial III and add dimethylchlorosilane (6.90 g, 0.074 mol) dropwise. Stir the reaction at room temperature for 12 hours. After completion of the reaction, quench the reaction with 10 ml of deionized water and pour the system into a large amount of n-hexane until a white precipitate forms. Collect the supernatant and remove the solvent by vacuum rotary evaporation to obtain the crude product. Purify the crude product by column chromatography (n-hexane as the developing solvent) to obtain a transparent, viscous liquid. Further purification by vacuum distillation yields pure DPE-SiH.

[0074] Step S2, synthesizing monomer DPE-2SiH:

[0075] 2.1) Under argon, dry methyltriphenylphosphonium bromide (30 g, 0.063 mol) was dissolved in 160 ml of dry THF. A THF solution of potassium tert-butoxide (7.67 g, 0.069 ml) (62 ml) was added dropwise to the reaction mixture. The reaction was stirred at -5°C for 2.5 h, followed by a THF solution of 4,4-dibromobenzophenone (9.47 g, 0.041 mol) (90 ml). The reaction was stirred at -20°C overnight. Upon completion, the reaction mixture exhibited an orange-red color. The reaction was quenched with 10 ml of deionized water, which immediately turned gray with the precipitation of an off-white precipitate. The salts were removed by filtration, and the supernatant was extracted with ethyl acetate and saturated sodium chloride solution to yield a light orange organic phase. Anhydrous magnesium sulfate was added to the organic phase, stirred, and the supernatant was collected. The solvent was removed by vacuum rotary evaporation to yield the crude product, which was purified by column chromatography (n-hexane as the developing solvent) to obtain DPE-2Br.

[0076] 2.2) Under inert gas, add DPE-2Br (31.95 g, 0.095 mol) and 215 ml of dry THF solution to Vial I and stir until ready for use. Add magnesium turnings, iodine pellets, dimethylsilyl chloride (26.43 g, 0.28 mol), and 215 ml of dry THF solution to Vial II, stir under reflux for 3 hours, and cool to room temperature until ready for use. Add the DPE-2Br solution from Vial I dropwise to Vial II. After the addition is complete, stir under reflux for 15 hours. After the reaction is complete, pour the mixture into n-hexane until a large amount of precipitate forms. Concentrate the filtrate by vacuum rotary evaporation and purify by column chromatography (n-hexane as the developing solvent) to obtain the crude product. Recrystallize the product from hot methanol to obtain pure DPE-2SiH.

[0077] Step S3, synthesizing a styrene-butadiene impact-resistant transparent resin functionalized with silicon groups having different chain initiation ends and chain termini:

[0078] Under nitrogen or argon protection, 2000g hexane, 0.1g 2,2-di(2-tetrahydrofuryl)propane and 0.2g DPE-SiH monomer were added to the polymerization reactor, the temperature was adjusted to 30°C, 1.5ml alkyl lithium initiator was added and the reaction was initiated for 5h, and monomers St (100g), Bd (15g), and Ip (10g) were added in sequence. The system was reacted at 50°C for 3h. After the monomer reaction was completed, 0.2g DPE-2SiH monomer was added to the polymerization reactor for end-capping. The system continued to react at 50°C for 1h. Finally, N-phenyl-α-naphthylamine (0.05g) was added, stirred evenly and discharged. The product number average molecular weight M n The molecular weight distribution index PDI is 1.10, the transparency is 85%, the haze is 5%, and the impact strength is 15kJ / m 2 .

[0079] Example 3

[0080] Step S1, synthesizing monomer DPE-SiH:

[0081] 1.1) Under nitrogen, dry methyltriphenylphosphonium bromide (50 g, 0.10 mol) and potassium tert-butoxide powder (12.72 g, 0.011 mol) were dissolved in 100 ml of dry THF and stirred at 0°C until the solution turned yellow. A THF solution (50 ml) of 4-bromobenzoylbenzene (20.20 g, 0.078 mol) was then added dropwise to the solution. The reaction was stirred at 0°C. After completion of the reaction, the solution exhibited an orange-red color. The solution was quenched with 15 ml of deionized water, which immediately faded to gray with the formation of an off-white precipitate. The solution was filtered to remove salt and the filtrate was extracted with ethyl acetate and saturated sodium chloride solution to obtain a light orange organic phase. Anhydrous magnesium sulfate was added to the organic phase, stirred, and the filtrate was collected. The solvent was removed by vacuum rotary evaporation to obtain a crude product, which was purified by column chromatography (n-hexane as the developing solvent) to obtain a colorless, transparent liquid, DPE-Br.

[0082] 1.2) Add DPE-Br (46.26 g, 0.18 mol) and 300 ml of dry THF to Vial I, seal the apparatus, and stir until ready for use. Add magnesium turnings and iodine granules to Vial II. Add a small amount of the liquid from Vial I dropwise to Vial II. Heat the system to initiate the reaction, then add the remaining liquid dropwise to the system. Stir the reaction under reflux for 3 hours, then cool until ready for use. Under nitrogen, transfer the supernatant from Vial II to Vial III and add dimethylchlorosilane (24.84 g, 0.27 mol) dropwise. Stir the reaction at room temperature for 12 hours. After completion of the reaction, quench the reaction with 20 ml of deionized water and pour the system into a large amount of n-hexane until a white precipitate forms. Collect the supernatant and remove the solvent by vacuum rotary evaporation to obtain the crude product. Purify the crude product by column chromatography (n-hexane as the developing solvent) to obtain a transparent, viscous liquid. Further purification by vacuum distillation yields pure DPE-SiH.

[0083] Step S2, synthesizing a styrene-butadiene impact-resistant transparent resin having the same silicon-containing functional group at the chain initiation end and the chain terminal:

[0084] Under nitrogen or argon protection, 2500g of methylcyclohexane, 0.15g of ethyltetrahydrofuranyl ether and 0.15g of DPE-SiH monomer were added to the polymerization reactor, the temperature was adjusted to 50°C, 2ml of alkyl lithium initiator was added and the reaction was initiated for 7h, and monomers St (80g), Bd (25g) and Ip (10g) were added in sequence. The system was reacted at 70°C for 6h. After the monomer reaction was completed, dichlorodimethylsilane (0.8g) was added to the polymerization reactor and the reaction was continued for 0.5h at a reaction temperature of 30°C. Finally, N,N'-diphenyl-p-phenylenediamine (0.08g) was added and the mixture was stirred evenly before discharging. The product number average molecular weight M nThe molecular weight distribution index PDI is 1.25, the transparency is 90%, the haze is 5%, and the impact strength is 20kJ / m 2 .

[0085] Example 4

[0086] Step S1, synthesizing the polymerization monomer DPE-2SiH:

[0087] 1.1) Under argon, dry methyltriphenylphosphonium bromide (60 g, 0.126 mol) was dissolved in 200 ml of dry THF. A solution of potassium tert-butoxide (15.34 g, 0.138 ml) in THF (100 ml) was added dropwise to the reaction mixture. The mixture was stirred at -5°C for 3 h, followed by a solution of 4,4-dibromobenzophenone (18.94 g, 0.082 mol) in THF (200 ml). The reaction was stirred at -20°C overnight. Upon completion, the reaction mixture exhibited an orange-red color. The mixture was quenched with 20 ml of deionized water, which immediately turned gray with the precipitation of an off-white precipitate. The salt was removed by filtration, and the supernatant was extracted with ethyl acetate and saturated sodium chloride solution to yield a light orange organic phase. Anhydrous magnesium sulfate was added to the organic phase, stirred, and the supernatant was collected. The solvent was removed by vacuum rotary evaporation to yield the crude product, which was purified by column chromatography (n-hexane as the developing solvent) to yield DPE-2Br.

[0088] 1.2) Under inert gas, add DPE-2Br (63.90 g, 0.19 mol) and 250 ml of dry THF solution to Vial I and stir until ready for use. Add magnesium turnings, iodine pellets, dimethylsilyl chloride (52.86 g, 0.56 mol), and 250 ml of dry THF solution to Vial II, stir under reflux for 5 hours, and cool to room temperature until ready for use. Add the DPE-2Br solution from Vial I dropwise to Vial II. After the addition is complete, stir under reflux for 24 hours. After the reaction is complete, pour the mixture into n-hexane until a large amount of precipitate forms. Concentrate the filtrate by vacuum rotary evaporation and purify by column chromatography (n-hexane as the developing solvent) to obtain the crude product. Recrystallize the product from hot methanol to obtain pure DPE-2SiH.

[0089] Step S2, synthesizing a styrene-butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain termination end:

[0090] Under nitrogen or argon protection, add 3000g cyclohexane and 0.15g diethylene glycol diethyl ether into the polymerization reactor, adjust the temperature to 90℃, add 3ml alkyl lithium initiator and initiate for 10h, then add St (100g), Bd (20g), Ip (25g) in sequence, and react the system at 110℃ for 10h. After the monomer reaction is completed, add dichlorodimethylsilane (1.2g) and DPE-2SiH (0.1g) into the polymerization reactor and continue to react for 5h at a reaction temperature of 110℃. Finally, add N-isopropyl-N'-phenyl-p-phenylenediamine (0.2g), stir evenly and discharge. The product number average molecular weight M n The molecular weight distribution index PDI is 1.50, the transparency is 95%, the haze is 3%, and the impact strength is 30kJ / m 2 .

[0091] Comparative Example 1 (Synthesis of a styrene-butadiene impact-resistant transparent resin containing no silicon group functionalization)

[0092] Under nitrogen or argon protection, add 1000g toluene and 0.1g tetrahydrofuran into the polymerization reactor, adjust the temperature to 10℃, add 1ml alkyl lithium initiator and initiate for 3h, then add monomers St (50g), Bd (10g), Ip (5g) in sequence, react at 30℃ for 1h, finally add 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (0.05g), stir evenly and discharge. The product number average molecular weight M n The molecular weight distribution index PDI is 1.13, the transparency is 65%, the haze is 45%, and the impact strength is 0.5kJ / m 2 .

[0093] Comparative Example 2 (Synthesis of a styrene-butadiene impact-resistant transparent resin containing no silicon group functionalization)

[0094] Synthesis of styrene-butadiene impact-resistant transparent resin without silicon group functionalization:

[0095] Under nitrogen or argon protection, add 2500g of methylcyclohexane and 0.15g of ethyl tetrahydrofurfuryl ether to the polymerization reactor, adjust the temperature to 50°C, add 2ml of alkyl lithium initiator and initiate for 7h, then add monomers St (80g), Bd (25g), and Ip (10g) in sequence, and react at 70°C for 6h. After the monomer reaction is completed, add dichlorodimethylsilane (0.1g) to the polymerization reactor and continue to react for 0.5h at a reaction temperature of 30°C. Finally, add N,N'-diphenyl-p-phenylenediamine (0.05g), stir evenly and discharge. The product number average molecular weight M n The molecular weight distribution index PDI is 1.25, the transparency is 60%, the haze is 30%, and the impact strength is 0.14kJ / m 2 .

[0096] Comparative Example 3 (Synthesis of a styrene-butadiene impact-resistant transparent resin containing no silicon group functionalization)

[0097] Under nitrogen or argon protection, add 3000g cyclohexane and 0.15g diethylene glycol diethyl ether to a polymerization reactor, adjust the temperature to 90°C, add 3ml alkyl lithium initiator and initiate for 10h, then add St (100g), Bd (20g), Ip (25g) in sequence, and react at 110°C for 10h. After the monomer reaction is completed, add dichlorodimethylsilane (0.25g) to the polymerization reactor and continue to react for 5h at a reaction temperature of 110°C. Finally, add N-isopropyl-N'-phenyl-p-phenylenediamine (0.05g), stir evenly and discharge. The product number average molecular weight M n The molecular weight distribution index PDI is 1.50, the transparency is 50%, the haze is 50%, and the impact strength is 0.8kJ / m 2 .

[0098] The above-described embodiments merely express the implementation methods of the present invention, but should not be understood as limiting the scope of the patent of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, which all fall within the scope of protection of the present invention.

Claims

1. A type of styrene-butadiene impact-resistant transparent resin functionalized with silicon groups at the chain ends, characterized in that: The said styrene-butadiene impact-resistant transparent resin with functionalized silicon groups at the chain ends is a block copolymer of styrene, butadiene, isoprene, and a 1,1-diphenylethylene derivative functionalized with silicon groups; Based on the mass of the end-silicon-functionalized styrene-butadiene impact-resistant transparent resin as 100%, the styrene content is 45% to 90%, the isoprene content is 0 to 15%, the content of the silicon-functionalized 1,1-diphenylethylene derivative is 0.2% to 2%, and the remainder is butadiene; The number average molecular weight M of the chain end silicon-containing functionalized styrene-butadiene impact-resistant transparent resin is n The range is 10,000 to 500,000, and the molecular weight distribution index PDI ranges from 1.02 to 1.

50.

2. The end-silicon-containing group functionalized styrene-butadiene impact-resistant transparent resin according to claim 1, characterized in that: The silicon-containing functionalized 1,1-diphenylethylene derivative is selected from diphenylethylene derivatives containing siloxy groups, silicon hydride groups and siloxy groups / silicon hydride groups; the siloxy groups, silicon hydride groups and siloxy groups / silicon hydride groups are connected to the para position, meta position or ortho position of the phenyl group in the 1,1-diphenylethylene derivative.

3. A method for preparing a styrene-butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the chain end as claimed in claim 2, characterized in that: The following steps are involved: S1. Under nitrogen or argon protection, add a measured amount of a non-polar solvent, a polarity regulator, and a silicon-containing functionalized 1,1-diphenylethylene derivative monomer into a polymerization reactor, adjust to a set temperature, add an alkyl lithium initiator according to the measured amount, the initiation temperature range is 10-90°C, the initiation time is 3-10 hours, then add styrene, butadiene, and isoprene in a set order, the reaction temperature is controlled at 30-110°C, and the reaction time is 1-10 hours; S2, preparing a butadiene-styrene impact-resistant transparent resin functionalized with a silicon group at the chain end, specifically selected from one of the following three operations: S21, adding a terminator and an antioxidant, stirring evenly and then discharging to prepare a styrene-butadiene impact-resistant transparent resin with a chain initiator end functionalized with a silicon group; S22. After the monomer reaction is completed, add a silicon-containing functionalized 1,1-diphenylethylene derivative monomer to the polymerization reactor for end-capping, the reaction temperature is 50-110° C., the reaction is continued for 1-3 hours, a terminator and an antioxidant are added, and the mixture is stirred evenly before discharging to obtain a butadiene-styrene impact-resistant transparent resin with silicon-containing functionalized chain initiation ends and chain termination ends; S23. Add a linear coupling agent to the polymerization reactor, continue the reaction for 0.5 to 5 hours, control the reaction temperature at 30-110°C, add a terminator and an antioxidant, stir evenly and then discharge the material to obtain a butadiene-styrene impact-resistant transparent resin functionalized with silicon groups at the chain ends, wherein both the chain initiation end and the chain termination end have 1,1-diphenylethylene derivative groups functionalized with silicon groups.

4. A method for preparing a styrene-butadiene impact-resistant transparent resin functionalized with a silicon-containing group at the end as claimed in claim 2, characterized in that: The following steps are involved: T1. Under nitrogen or argon protection, add the measured non-polar solvent and polarity regulator into the polymerization reactor, adjust to the set temperature, add the alkyl lithium initiator according to the measured amount, the initiation temperature range is 10-90°C, and the initiation time is 3-10 hours; add the reaction monomers styrene, butadiene, and isoprene, control the reaction temperature at 30-110°C, and the reaction time is 1-10 hours; T2. Add a linear coupling agent to the polymerization reactor and continue the reaction for 0.5 to 5 hours. The reaction temperature is controlled at 30-110°C. Add a silicon-containing group-functionalized 1,1-diphenylethylene derivative monomer to the polymerization reactor for end-capping. The reaction temperature is 50-110°C. The reaction is continued for 1 to 3 hours. Add a terminator and an antioxidant, stir evenly, and then discharge the material to obtain the butadiene-styrene impact-resistant transparent resin with silicon-containing group functionalized on the chain end; wherein the chain terminator has a silicon-containing group-functionalized 1,1-diphenylethylene derivative group.

5. The preparation method according to any one of claims 3 or 4, characterized in that The molar ratio of the total amount of the silicon-containing functionalized 1,1-diphenylethylene derivative added in at least one step to the alkyl lithium initiator is (1-5):1, and the mass ratio of styrene, butadiene, and isoprene is (0.8-1.6):1:(0-0.3).

6. The preparation method according to any one of claims 3 or 4, characterized in that The molar ratio of the polarity regulator to the alkyl lithium initiator is (0.5-5):1; The molar ratio of the linear coupling agent to the alkyl lithium initiator is (1-3):1; the molar ratio of the terminator to the alkyl lithium initiator is (1-10):

1.

7. The preparation method according to any one of claims 3 or 4, characterized in that The mass fraction of the three reaction monomers of styrene, butadiene and isoprene in the solution is 5-20%; the mass ratio of the antioxidant to the three reaction monomers of styrene, butadiene and isoprene is 1:(1000-10000), and the mass ratio of the antioxidant to the three reaction monomers of styrene, butadiene and isoprene is 1:(1000-10000).

8. The preparation method according to any one of claims 3 or 4, characterized in that The non-polar solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, methylcyclohexane, mixed aromatic hydrocarbons, and mixed aliphatic hydrocarbons.

9. The preparation method according to any one of claims 3 or 4, characterized in that The alkyl lithium initiator is selected from n-butyl lithium and sec-butyl lithium.

10. The preparation method according to any one of claims 3 or 4, characterized in that The polarity regulator is tetrahydrofuran, 2,2-bis(2-tetrahydrofuranyl)propane, 2,2-bis(5-methyl-2-tetrahydrofuranyl)propane, ethyl tetrahydrofuranyl ether, tetramethylethylenediamine, and diethylene glycol diethyl ether; The oxidant is selected from 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), β-(3.5-di-tert-butyl, 4-hydroxyphenyl) propionate, and 2,6-di-tert-butylphenol.

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