Amino-functionalized high-impact polystyrene in star chain and preparation method and application thereof

Abstract

This invention discloses a type of star-shaped chain amino-functionalized high-impact polystyrene, its preparation method, and its applications. The material is an in-situ composite composed of a C-(fSBC-fPS)n structured star-shaped polybutadiene / chain amino-functionalized styrene copolymer and a C-(fPS)n structured star-shaped chain amino-functionalized styrene copolymer. Wherein, fSBC is a butadiene / styrene / amino-functionalized DPE derivative copolymer, fPS is a styrene / amino-functionalized DPE derivative copolymer, and C is a multifunctional alkyl lithium initiator residue. This invention employs an in-situ batch method, qualitatively, quantitatively, and locally introducing amino groups into the rubber and resin phases via anionic polymerization, and constructing a star-shaped topology using a multifunctional initiator. This technical solution significantly improves the interfacial compatibility between the rubber and resin phases, greatly enhances the material's impact resistance, achieving an Izod notched impact strength of no less than 274 J / m, while maintaining excellent processing fluidity. This material can be widely used in high-impact injection-molded products such as electronic and electrical housings and automotive interiors.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer materials technology, and relates to a type of star-shaped chain amine-functionalized high-impact polystyrene, its preparation method and application. Background Technology

[0002] High-impact polystyrene (HIPS) is a polymeric material composed of toughening rubber as the dispersed phase (rubber phase) and polystyrene resin as the matrix phase (resin phase). The toughening rubber is often made of polybutadiene rubber or styrene-butadiene copolymer rubber, typically prepared using solution polymerization methods. Examples include linear and star-shaped low-cis polybutadiene rubbers prepared by anionic solution polymerization using alkyl lithium as an initiator; and high-cis polybutadiene rubbers prepared by coordination solution polymerization using cobalt-based Zn catalysts. HIPS is usually prepared using a free radical polymerization mechanism (R-HIPS), and currently, most are produced using a bulk continuous process, as represented by companies like Dow and BASF. This process involves first dissolving the toughening rubber (polybutadiene rubber or styrene-butadiene copolymer rubber) into styrene, and then initiating polymerization through heat or an initiator. The preparation process is divided into two parts: the production of the toughening rubber and the production of the polystyrene resin, generally requiring separate units. Toughened rubber production requires post-processing steps such as solvent removal, extrusion drying, and packaging molding, while polystyrene resin production requires rubber cutting and dissolving in styrene. Furthermore, the free radical polymerization process for styrene has drawbacks, including the necessity of monomer recovery, the inability to synthesize star polymers, the tendency to generate styrene oligomers during polymerization, low molecular weight with a wide molecular weight distribution, and a large amount of residual monomer.

[0003] Leng Xuefei et al. provided a method for preparing HIPS resin by toughening with functionalized lithium-based rubber (CN117186311 A). This invention uses an appropriate amount of aromatic hydrocarbon as a solvent and employs a living anionic polymerization method to prepare a functionalized lithium-based rubber solution without post-treatment. Styrene monomer is then added, and HIPS resin is prepared via free radical polymerization. This invention combines the two independent units of synthesizing toughening rubber and synthesizing resin into one, significantly shortening the preparation process of HIPS resin in actual production and improving production efficiency. The product has a narrow molecular weight distribution and uniform gloss, while reducing the gel content of the lithium-based rubber. It also increases the functional group insertion rate, as well as the grafting rate and compatibility between the toughening rubber and the resin matrix, thereby significantly improving the impact resistance of the HIPS resin.

[0004] BASF has successfully prepared high-impact polystyrene (A-HIPS) using restricted anionic polymerization [Philippe Desbois, Volker Warzelhan, et al., Anionic High Impact Polystyrene: A New Process for Low Residual and Low Cost HIPS, Macromolecular Symposia, 2006, 240: 194-205]. Li Yang et al. disclosed a star-shaped high-impact polystyrene and its preparation method, as well as a star-shaped high-impact butadiene / isoprene / styrene terpolymer resin and its preparation method. This method integrates the production processes of toughened rubber and polystyrene resin into a single unit using an in-situ bulk polymerization. Based on anionic polymerization, toughened rubber is first prepared in situ, followed by polystyrene production. This simplifies the production process of high-impact polystyrene resin, eliminating the three post-processing stages (solvent removal, extrusion drying, and packaging) required for toughened rubber production, as well as the two stages (rubber cutting and dissolving) required for polystyrene resin production, significantly improving production efficiency. Because high-impact polystyrene resin is prepared directly from styrene rubber in situ, the extrusion drying post-processing stage is eliminated, effectively controlling gel formation in the toughened rubber and improving the quality of the high-impact polystyrene resin product.

[0005] However, existing technologies still have the following shortcomings:

[0006] In the traditional HIPS production process, the synthesis of toughened rubber and the preparation of polystyrene resin are two separate steps. This not only increases the complexity of the process, but also easily leads to efficiency loss in the connection between the two processes, affecting the overall production efficiency.

[0007] Although existing HIPS preparation methods can enhance the impact resistance of materials to some extent, their impact resistance is still insufficient for higher standard applications, such as electronic device housings and automotive parts, especially in terms of durability under extreme conditions.

[0008] Within the existing technological framework, the compatibility issue between HIPS materials and various polar additives has not been fundamentally resolved. This leads to phase separation when specific functional additives are added, affecting the overall performance of the material. Furthermore, the processing properties of the material, including flowability and thermal stability, are often limited by constraints in formulation and structural design.

[0009] Traditional preparation methods often rely on a single polymerization technique, which has a weak ability to precisely control complex structures. For example, it is difficult to effectively form star-shaped chain structures with special functional groups, which limits the innovation of material structure and the potential performance improvement it brings.

[0010] Given the aforementioned issues, existing HIPS fabrication technologies cannot fully meet the market's urgent demands for high performance, high efficiency, and ease of processing. These technological limitations are particularly prominent today, especially as the pursuit of multifunctional and customized materials is intensified. Summary of the Invention

[0011] To address the problems existing in the prior art, this invention proposes a new technology for the in-situ and efficient preparation of star-chain amine-functionalized high-impact polystyrene by qualitative, quantitative, and localized functionalization modification of toughened rubber and polystyrene resin. This technology involves the preparation method of a type of star-chain amine-functionalized high-impact polystyrene.

[0012] The technical features of this invention are as follows: (1) In-situ batch method is used to prepare high-impact polystyrene with functionalized star-shaped chains. The preparation of toughened rubber and polystyrene resin is completed in the same unit, which simplifies the production process of high-impact polystyrene resin and greatly improves production efficiency. (2) Based on anionic polymerization method, by qualitatively, quantitatively and locally introducing comonomers with amino groups in the chain into the rubber phase and resin phase, the functionalized groups are more evenly distributed in the polymer chain, the rubber phase and resin phase have good compatibility, and the material has excellent impact resistance. Introducing amino functional groups into the resin phase can also greatly improve the binding and compatibility of the material with polar additives. (3) Using multifunctional alkyl lithium as an initiator, the introduction of star structure can give the material good processing performance and higher melt strength. Compared to end-chain amine functionalization, the in-chain amine functionalization employed in this invention involves the controlled insertion of DPE derivatives during polymerization, resulting in a uniform distribution of amine groups along the polymer backbone. This avoids the aggregation of functional groups into clusters, thereby more effectively improving the interfacial compatibility between the rubber and resin phases and enhancing the interaction with polar additives. This invention is the first to achieve a three-in-one approach: "star structure + in-chain amine functionalization + simultaneous functionalization of both rubber and resin phases," enabling simultaneous control of the degree of amine functionalization in both the rubber and resin phases within a star-shaped HIPS.

[0013] The technical solution of the present invention is as follows:

[0014] A class of star-shaped chain amino-functionalized high-impact polystyrene is characterized by C-(fSBC-fPS). n Star-shaped polybutadiene / in-chain amino-functionalized styrene copolymers with C-(fPS) structure nAn in-situ complex of an amino-functionalized styrene copolymer in a star-shaped chain structure, wherein fSBC is a butadiene / styrene / amino-functionalized DPE derivative copolymer, C-(fSBC-fPS). n and C-(fPS) n The fPS in this text are all styrene / amine-functionalized DPE derivative copolymers. They have different compositions and molecular weights and are independent of each other. C represents a multifunctional alkyl lithium initiator residue, and n represents the functionality of the multifunctional initiator, with a value not less than 3, more preferably 3-10, and most preferably n is... ;

[0015] The material has an Izod notched impact strength ≥274 J / m and a melt flow index of [missing value]. .

[0016] For the technical solution described above, more preferably, based on the total polymer mass of amino-functionalized high-impact polystyrene in the star-shaped chain being 100%, the mass fraction of butadiene structural units is 10-25%, preferably 14-25%, the mass fraction of amino-functionalized DPE derivative structural units is 1-10%, preferably 4.5-10%, and the remainder is styrene structural units; and, C-(fPS) n The number-average molecular weight is 5.6 × 10⁻⁶. 4 -30.5×10 4 g / mol, more preferably Based on 100% fSBC mass, the styrene content in fSBC is 5-20%, preferably 13-20%, the amino-functionalized DPE derivative content is 1-10%, preferably 5-9.5%, and the remainder is butadiene. The number-average molecular weight of the single arm of fSBC is 5 × 10⁻⁶. 4 -20.2×10 4 More preferably .

[0017] Furthermore, regarding the technical solution described above, the amino-functionalized DPE derivative is a derivative in which an N,N-dialkylamine substituent is introduced at the para position of the benzene ring of the 1,1-diphenylethylene (DPE) skeleton, wherein the number of the substituent is one or two; the N,N-dialkylamine is N,N-dimethyl, N,N-diethyl or N,N-di-tert-butyl.

[0018] More preferably, the amino-functionalized DPE derivative is selected from one or more of the following compounds: 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene, 1,1'-bis[4-(N,N-diethylamino)phenyl]ethylene, 1,1'-bis[4-(N,N-di-tert-butylamino)phenyl]ethylene, 1-[4-(N,N-dimethylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-diethylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-di-tert-butylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-trimethylsilylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-methyltrimethylsilylamino)phenyl]-1'-phenylethylene, or one or more amino-functionalized monomers selected from the following groups.

[0019] For the technical solution described above, more preferably, the fSBC is selected from one or a mixture of several polymers selected from block butadiene / in-chain amino functionalized styrene copolymers, gradient block butadiene / in-chain amino functionalized styrene copolymers, and random block butadiene / in-chain amino functionalized styrene copolymers, or is a multi-block copolymer composed of the above polymers. More preferably, the fSBC is a butadiene-styrene copolymer containing in-chain amino groups obtained by living anionic polymerization, and its microstructure is block or gradient block.

[0020] Secondly, the present invention provides a method for preparing the above-described star-shaped chain amine-functionalized high-impact polystyrene, comprising the following steps:

[0021] S1. Under nitrogen or argon protection, nonpolar hydrocarbon solvent, functional monomer activator, butadiene monomer, first batch of styrene monomer, and amino-functionalized DPE derivative are added to the reactor in the specified proportions. A multifunctional alkyl lithium initiator is added for the first time. The reaction temperature is 30-70℃ and the reaction time is 1-5 hours to prepare C-(fSBC). n The amount of the multifunctional alkyl lithium initiator added for the first time is determined according to the number-average molecular weight of the fSBC single arm; the molar ratio of the functional monomer activator to the multifunctional alkyl lithium initiator is 1-100;

[0022] S2. Add an optional anionic polymerization retarder, which is selected from one or more alkyl metal compounds, and the molar ratio of the retarder to the multifunctional alkyl lithium initiator (the sum of the first and the set second addition amounts) is 0.3-0.9.

[0023] S3. Add the second batch of styrene monomer and amino-functionalized DPE derivative to the reactor according to the formula. Add the multifunctional alkyl lithium initiator for the second time. The amount of multifunctional alkyl lithium initiator added for the second time is based on the C- (fPS) of star-shaped polystyrene. n The molecular weight is determined by the design; the reaction temperature is 30-70℃, and the reaction time is 2-5 hours to prepare C-(fPS). n Meanwhile, C-(fSBC) n The chain segment continues to grow, generating C-(fSBC-fPS). n According to the principle of anionic polymerization, the molecular weight of the polymer can be designed; molecular weight = monomer mass / initiator concentration.

[0024] For the technical solution described above, a further preferred embodiment is that the multifunctional alkyllithium initiator is selected from any multifunctional alkyllithium initiator disclosed in the prior art that can be used in anionic polymerization systems, and can be one multifunctional alkyllithium initiator or a mixture of several multifunctional alkyllithium initiators, such as the general formula RLi. n As shown, R is a hydrocarbon group with 4-20 carbon atoms, such as an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and n is the functionality of the initiator and its value is greater than or equal to 3. The value of n is generally 3-50, the preferred range is 3-10, and the most preferred value of n is 3-5.

[0025] For the technical solution described above, a further preferred embodiment is the multifunctional alkyl lithium initiator RLi. n It can be a multi-chelate organolithium initiator, such as the various multi-chelate organolithium initiators obtained by reacting divinylbenzene (DVB) with alkyllithium mentioned in patents such as GB2124228A, US3280084, EP0573893A2, and CN1197806A. The alkyllithium initiator is generally selected from butyllithium. The multifunctional alkyllithium initiator can also be other multifunctional alkyllithium initiators with a functionality of not less than 3 that can be used to initiate the polymerization of conjugated diene monomers such as butadiene and isoprene, and styrene monomers, such as the various multifunctional alkyllithium initiators mentioned in patents US5262213 and US5595951. More preferably, the functionality n is 3-10, and most preferably, n is 3-5. The most preferred embodiment uses a multi-chelate m-Li with a functionality range of 3–5.

[0026] For the technical solution described above, a further preferred embodiment is that the anionic polymerization inhibitor is selected from any anionic polymerization inhibitor disclosed in the prior art that can be used in alkyl lithium initiation systems, and can be one anionic polymerization inhibitor or a mixture of several anionic polymerization inhibitors, generally selected from alkyl metal compounds such as alkyl magnesium, alkyl barium, and alkyl aluminum, preferably from alkyl aluminum. The alkyl aluminum used in this invention is selected from any alkyl aluminum disclosed in the prior art that can be used as an anionic polymerization inhibitor, and can be one alkyl aluminum or a mixture of several alkyl aluminums, generally selected from one or a mixture of several alkyl aluminums selected from: trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tritert-butylaluminum, and tributylaluminum, preferably from: triethylaluminum and triisobutylaluminum.

[0027] For the technical solution described above, it is further preferred that the functional monomer activator is added in order to regulate the structure of butadiene segment 1,2, change the reactivity ratio of butadiene / styrene, realize butadiene / styrene block copolymerization, regulate the polymer activity of diphenylethylene derivatives and their distribution in the polymer chain. The functional monomer activator used is selected from one or a mixture of several compounds including oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and alkoxy metal compounds, such as: (1) oxygen-containing compounds, generally selected from: diethyl ether, tetrahydrofuran, R1OCH2CH2OR2 (where R1 and R2 are alkyl groups with 1-6 carbon atoms, which can be the same or different, and it is preferred that R1 and R2 are different, such as: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2 (where R1 and R2 are alkyl groups with 1-6 carbon atoms). Alkyl groups can be the same or different, with different R1 and R2 being preferred, such as: diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ether; (2) Nitrogen-containing compounds, generally selected from: triethylamine, tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE); (3) Phosphorus-containing compounds, generally selected from: hexamethylphosphoric triamine (HMPA); (4) Alkoxy metal compounds, generally selected from ROM, where: R is an alkyl group with 1-6 carbon atoms, O is an oxygen atom, and M is sodium or potassium metal, preferably from: potassium tert-butoxy and potassium tert-pentoxy.

[0028] For the technical solution described above, a further preferred embodiment is that the nonpolar hydrocarbon solvent is selected from one or a mixture of several nonpolar aromatic hydrocarbons and nonpolar aliphatic hydrocarbons, generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (such as mixed xylenes), mixed aliphatic hydrocarbons (such as raffinate oil), etc., preferably selected from: hexane, cyclohexane, and raffinate oil. The mass ratio of the solvent to all monomers is 0.3-0.5. In the phrase "mass ratio of nonpolar hydrocarbon solvent to all monomers 0.3-0.5", "all monomers" refers to the sum of the masses of butadiene, the first addition of styrene, the first addition of DPE derivative, the second addition of styrene, and the second addition of DPE derivative.

[0029] Another aspect of this invention protects the application of the amine-functionalized high-impact polystyrene in the star-shaped chain in the preparation of injection-molded articles and in the preparation of high-impact polystyrene blends.

[0030] Preferably, the injection-molded product is an electronic appliance housing, an automotive interior component, or a household appliance housing; or the blend is composed of general-purpose polystyrene (GPPS) or high-impact polystyrene (HIPS) and 5–30 wt% of the star-shaped chain amine-functionalized high-impact polystyrene, and its Izod notched impact strength is ≥ 250 J / m.

[0031] The beneficial effects of this invention are as follows:

[0032] (1) The star-shaped chain functionalized high-impact polystyrene was prepared by in-situ batch method. The preparation of toughened rubber and polystyrene resin was completed in the same unit, which simplified the production process of high-impact polystyrene resin and greatly improved the production efficiency. (2) Based on the anionic polymerization method, the functionalized groups were introduced into the rubber phase and resin phase in a qualitative, quantitative and positional manner by the comonomer. The functionalized groups were more evenly distributed in the polymer chain. The rubber phase and resin phase had good compatibility, which gave the material excellent impact resistance. The introduction of amine functional groups into the resin phase can also greatly improve the binding and compatibility of the material with polar additives. (3) Using multifunctional alkyl lithium as an initiator, the introduction of star structure can give the material good processing performance and higher melt strength. Detailed Implementation

[0033] The present invention provides the following embodiments as further illustration, but does not limit the scope of protection of the claims of the present invention.

[0034] The solvents, monomers, initiators, auxiliaries and additives used in the various embodiments of the present invention are all commercially available industrial grade or chemically pure or higher reagents. Unless otherwise specified, they are all dried and purified according to conventional requirements in the art. The analytical and characterization methods used, such as nuclear magnetic resonance, infrared spectroscopy, gel permeation chromatography, mechanical property testing and melt index determination, are all standard methods known and commonly used in the art. Those skilled in the art can directly implement them according to conventional experimental conditions.

[0035] The multifunctional alkyl lithium initiator used in the following examples is a polychelate alkyl lithium initiator (m-Li), and the synthesis method can be found in the literature [Wang Yanse, Zhang Yueyuan, Wu Jiahong, Shen Kaihua, Li Yang, Application of Restricted Anionic Polymerization I. Preparation and Impact Resistance of Star-shaped High-Impact Polystyrene, Synthetic Resins and Plastics. 2015, 32 (04), 1-5]. The specific preparation method of the polychelate alkyl lithium initiator (m-Li) is as follows: Under nitrogen protection, purified cyclohexane and divinylbenzene (DVB) are added to a dry and deoxygenated reactor, the temperature is raised to 30~50℃, and sec-butyllithium (sec-BuLi) is slowly added dropwise under stirring. The molar ratio of DVB to sec-BuLi is 1:3.0~1:3.5. After the addition is complete, the reaction continues for 2~4 hours to obtain an orange-red homogeneous solution. The concentration of active lithium is determined by double titration, and its average functionality is calculated to be 3.0~4.0. The initiator has a multi-arm star structure, which can simultaneously initiate the growth of multiple polymer chains. It is the key to achieving structural control of functionalized high-impact polystyrene in star chains.

[0036] The compositional sequence distribution and microstructure of the copolymer were analyzed using nuclear magnetic resonance spectroscopy and infrared spectroscopy. The molecular weight and molecular weight distribution index of the copolymer were analyzed using gel permeation chromatography. The tensile strength, elongation at break and impact strength of the material were determined using a material testing machine and an impact tester. The melt index of the material was determined using a melt indexer.

[0037] Example 1

[0038] In a stirred stainless steel reactor, 40 g of cyclohexane, 15 g of butadiene (Bd), 2.5 g of styrene (St1), and 1.0 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt1) were added. The mixture was heated to 50 °C, and 0.185 mmol of m-Li initiator (n=3.4) was added. The reaction was allowed to proceed for 3 hours. Then, 0.356 mmol of triisobutylaluminum was added, followed by 78.0 g of styrene (St2) and 3.5 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt2). After thorough mixing, 0.408 mmol of m-Li initiator (n=3.4) was added, and the reaction was continued at 50 °C for another 3 hours. Finally, 0.5 mL of isopropanol and an antioxidant (BASF's Irganox) were added. 1 gram of 1010 and 2,6-di-tert-butyl-p-cresol were mixed in a 1:1 weight ratio. The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is 10.3 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 19.7 × 10⁻⁶. 4 The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 382.9 J / m, and the melt index is 13.7 g / 10 min (220℃, 10 kg).

[0039] Example 2

[0040] In a stirred stainless steel reactor, 30 g toluene, 14 g butadiene (Bd), 3.7 g styrene (St1), 1.0 g 1,1'-bis[4-(N,N-diethylamino)phenyl]ethylene (fSt1), and 0.04 mmol potassium tert-butoxy were added. The mixture was heated to 40 °C, and 0.187 mmol of m-Li initiator (n=3.4) was added. The reaction was allowed to proceed for 4 hours. 0.412 mmol of trimethylaluminum was then added, followed by 72.3 g styrene (St2) and 9.0 g 1,1'-bis[4-(N,N-diethylamino)phenyl]ethylene (fSt2). After thorough mixing, 0.271 mmol of m-Li initiator (n=3.4) was added, and the reaction was continued at 40 °C for another 4 hours. 0.5 mL of isopropanol and an antioxidant (BASF's Irganox) were then added. 1 gram of 1010 and 2,6-di-tert-butyl-p-cresol were mixed in a 1:1 weight ratio. The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is 10.1 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 30.5 × 10⁻⁶. 4The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 397.5 J / m, and the melt index is 12.5 g / 10 min (220℃, 10 kg).

[0041] Example 3

[0042] In a stirred stainless steel reactor, 35 g benzene, 10 g butadiene (Bd), 1.0 g styrene (St1), 0.2 g 1-[4-(N,N-dimethylamino)phenyl]-1'-phenylethylene (fSt1), and 0.05 mmol potassium tert-pentoxy were added. The mixture was heated to 30 °C, and 0.056 mmol of m-Li initiator (n=3.9) was added. The reaction was allowed to proceed for 5 hours. 0.550 mmol of triethylaluminum was then added, followed by 88.0 g styrene (St2) and 0.8 g 1-[4-(N,N-dimethylamino)phenyl]-1'-phenylethylene (fSt2). After thorough mixing, 1.776 mmol of m-Li initiator (n=3.9) was added, and the reaction was continued at 30 °C for another 5 hours. 0.5 mL of isopropanol and an antioxidant (BASF's Irganox) were then added. 1 gram of 1010 and 2,6-di-tert-butyl-p-cresol were mixed in a 1:1 weight ratio. The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is 20.2 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 5.6 × 10⁻⁶. 4 The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 274.3 J / m, and the melt index is 13.0 g / 10 min (220℃, 10 kg).

[0043] Example 4

[0044] In a stirred stainless steel reactor, 45 g benzene, 25 g butadiene (Bd), 5.0 g styrene (St1), and 0.3 g 1-[4-(N,N-di-tert-butylamino)phenyl]-1'-phenylethylene (fSt1) were added. The mixture was heated to 70 °C, and 0.506 mmol of m-Li initiator (n=3.9) was added. The reaction was allowed to proceed for 1 hour. Then, 0.249 mmol of triisobutylaluminum was added, followed by 64.7 g styrene (St2) and 5.0 g 1-[4-(N,N-di-tert-butylamino)phenyl]-1'-phenylethylene (fSt2). After thorough mixing, 0.299 mmol of m-Li initiator (n=3.9) was added, and the reaction was continued at 70 °C for 2 hours. Finally, 0.5 mL of isopropanol and an antioxidant (BASF's Irganox) were added. 1 gram of 1010 and 2,6-di-tert-butyl-p-cresol were mixed in a 1:1 weight ratio. The adhesive was then post-treated and dried using conventional methods. C-(fSBC)n The molecular weight of the single arm is 6.0 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 23.6 × 10⁻⁶. 4 The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 453.6 J / m, and the melt index is 13.5 g / 10 min (220℃, 10 kg).

[0045] Example 5

[0046] In a stirred stainless steel reactor, add 50 g of toluene / benzene (1:1) mixed solution, 20 g of butadiene (Bd), 4.0 g of styrene (St1), and 2.5 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt1). Heat to 40 °C, add 0.177 mmol of m-Li initiator (n=4.9), and react for 2 hours. Add 0.4 mmol of triisobutylaluminum, then add 70.5 g of styrene (St2) and 3.0 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt2). After stirring and mixing thoroughly, add 0.49 mmol of m-Li initiator (n=4.9), adjust the temperature to 60 °C, and continue reacting for 3 hours. Add 0.5 mL of isopropanol and an antioxidant (BASF's Irganox). 1 gram of 1010 and 2,6-di-tert-butyl-p-cresol were mixed in a 1:1 weight ratio. The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is 15.3 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 15.9 × 10⁻⁶. 4 The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 427.4 J / m, and the melt index is 11.9 g / 10 min (220℃, 10 kg).

[0047] Comparative Example 1 (functionalized toughened rubber, unmodified resin phase, free radical polymerization)

[0048] Under nitrogen protection, 170 mL of o-xylene solvent and 3 g of 1-[4-(dimethylsilyl)phenyl]-1-phenylethylene were added sequentially to a dried and deoxygenated polymerization reactor. Anionic polymerization was carried out, and the temperature was raised to 30 °C, according to the designed molecular weight of 20 × 10⁻⁶. 4 Add g / mol of n-butyllithium initiator, react for 60 min, then add 20 g of butadiene and 10 g of styrene, react for 3 h to prepare functionalized styrene-butadiene rubber (SBR) solution. The product structure analysis results are as follows: the number average molecular weight of the functionalized SBR is 19.4 × 10⁻⁶ g / mol. 4The product has a molecular weight distribution of 1.09; the butadiene content in the rubber is 60.8% by mass, the styrene content is 30.0% by mass, and the 1[4-(dimethylsilyl)phenyl]-1-phenylethylene content is 9.2% by mass; the adhesive concentration is 15.0%. In a 2L stainless steel reactor with a stirrer, the synthesized functionalized styrene-butadiene rubber adhesive and 570g of styrene were added. After stirring evenly, the temperature was raised to 105℃, and free radical polymerization was carried out. 180mg of 1,1-di(tert-butyl peroxide)cyclohexane was added, and the temperature was gradually raised to 140℃. The reaction was carried out for 6 hours. After the reaction, the polymer was post-treated using conventional methods. The product structure analysis results are as follows: the polystyrene content in the product is 73.5% by mass, the functionalized styrene-butadiene rubber content is 16.5% by mass, and the number average molecular weight is 24.1×10⁻⁶. 4 g / mol, molecular weight distribution is 2.2; Izod impact strength is 210.3 J / m, melt index is 9.5 g / 10 min (220℃, 10 kg).

[0049] Comparative Example 2 (Anionic polymerization, without functional groups)

[0050] In a stirred stainless steel reactor, 50 g of toluene / benzene (1:1) mixed solution, 20 g of butadiene (Bd), and 4.0 g of styrene (St1) were added. The mixture was heated to 40°C, and 0.177 mmol of m-Li initiator (n=4.9) was added. The reaction was allowed to proceed for 2 hours. Then, 0.4 mmol of triisobutylaluminum was added, followed by 70.5 g of styrene (St2). After thorough mixing, 0.49 mmol of m-Li initiator (n=4.9) was added, and the temperature was adjusted to 60°C. The reaction was continued for 3 hours. 0.5 mL of isopropanol was added, along with 1 g of antioxidant (a 1:1 mixture of BASF's Irganox 1010 and 2,6-di-tert-butyl-p-cresol by weight). The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is 13.9 × 10⁻⁶. 4 g / mol, C-(fPS) n The molecular weight of the single arm is 14.2 × 10⁻⁶. 4 The impact strength of functionalized high-impact polystyrene in the star-shaped chain is 320.6 J / m, and the melt index is 10.9 g / 10 min (220℃, 10 kg).

[0051] Comparative Example 3 (Linear Structure + DPE Functionalization)

[0052] In a stirred stainless steel reactor, 40 g of cyclohexane, 15 g of butadiene (Bd), 2.5 g of styrene (St1), and 1.0 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt1) were added. The mixture was heated to 50 °C, and 0.185 mmol of n-butyllithium (n-BuLi) initiator was added. The reaction was carried out for 3 hours, followed by 0.356 mmol of triisobutylaluminum, 78.0 g of styrene (St2), and 3.5 g of 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene (fSt2). After stirring and mixing thoroughly, 0.408 mmol of n-BuLi initiator was added, and the reaction was continued at 50 °C for another 3 hours. 0.5 mL of isopropanol was added, along with 1 g of antioxidant (a mixture of BASF's Irganox 1010 and 2,6-di-tert-butyl-p-cresol in a 1:1 weight ratio). The adhesive was then post-treated and dried using conventional methods. C-(fSBC) n Its molecular weight is 10.1 × 10⁻⁶. 4 g / mol, C-(fPS) n Its molecular weight is 20.1 × 10⁻⁶. 4 The impact strength of the functionalized high-impact polystyrene in the chain is 292.9 J / m, and the melt index is 9.4 g / 10 min (220℃, 10 kg).

[0053] Comparative Example 4 (star structure, without amine functionalization)

[0054] In a stirred stainless steel reactor, 50 g of toluene / benzene (1:1) mixed solution, 20 g of butadiene (Bd), and 4.0 g of styrene (St1) were added, without any amino-functionalized DPE derivatives. The mixture was heated to 40 °C, and 0.177 mmol of m-Li initiator (n=4.9) was added. The reaction was allowed to proceed for 2 hours. Then, 0.4 mmol of triisobutylaluminum was added, followed by 70.5 g of styrene (St2). Again, without any amino-functionalized DPE derivatives, the mixture was stirred until homogeneous. Then, 0.49 mmol of m-Li initiator (n=4.9) was added, and the temperature was adjusted to 60 °C. The reaction was continued for 3 hours. 0.5 mL of isopropanol was added, along with 1 g of antioxidant (a 1:1 mixture of BASF's Irganox 1010 and 2,6-di-tert-butyl-p-cresol). The resin was then post-treated and dried using conventional methods. C-(fSBC) n The molecular weight of the single arm is C-(fPS) n The molecular weight of the single arm is The Izod notched impact strength of star-shaped high-impact polystyrene is 313.6 J / m, and the melt flow index is 10.7 g / 10min (220℃, 10kg).

[0055] The above-described embodiments are merely illustrative of the implementation methods of the present invention, but should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the protection scope of the present invention.

Claims

1. A class of star chain aminofunctionalized high-impact polystyrene characterized in that: It is an in-situ composite of a star-shaped polybutadiene / in-chain amino-functionalized styrene copolymer with a C-(fSBC-fPS)n structure and a star-shaped in-chain amino-functionalized styrene copolymer with a C-(fPS)n structure, wherein fSBC is a butadiene / styrene / amino-functionalized DPE derivative copolymer, and fPS in C-(fSBC-fPS)n and C-(fPS)n are both styrene / amino-functionalized DPE derivative copolymers. The two have different compositions and molecular weights and are independent of each other. C is a multifunctional alkyl lithium initiator residue, and n is the functionality of the multifunctional initiator, and its value is not less than 3. The material has an Izod notched impact strength ≥274 J / m and a melt flow index of 11.9 g / 10min to 13.7 g / 10min at 220℃ and 10 kg.

2. The type of star-shaped chain amino-functionalized high-impact polystyrene according to claim 1, characterized in that: The mass fraction of butadiene structural units is 0.1-10% based on 100% of the total mass of the amine group functionalized high-impact polystyrene in the star chain ; the mass fraction of amine group functionalized DPE derivative structural units is 0.1-10% ; the rest is a styrene structural unit; and the number average molecular weight of C-(fPS)n is ; the mass proportion of styrene in fSBC is 90-100% based on 100% of the mass of fSBC ; the mass proportion of amine group functionalized DPE derivative is 1-10%. The remainder is butadiene, and the number-average molecular weight of the fSBC single arm is [missing value]. .

3. The type of star-shaped chain amino-functionalized high-impact polystyrene according to claim 1, characterized in that: The amino-functionalized DPE derivative is a derivative in which an N,N-dialkylamine substituent is introduced at the para position of the benzene ring of the 1,1-diphenylethylene skeleton, wherein the number of the substituent is one or two; the N,N-dialkylamine is N,N-dimethyl, N,N-diethyl or N,N-di-tert-butyl.

4. The type of star-shaped chain amino-functionalized high-impact polystyrene according to claim 1, characterized in that: The amino-functionalized DPE derivatives are selected from one or more of the following compounds: 1,1'-bis[4-(N,N-dimethylamino)phenyl]ethylene, 1,1'-bis[4-(N,N-diethylamino)phenyl]ethylene, 1,1'-bis[4-(N,N-di-tert-butylamino)phenyl]ethylene, 1-[4-(N,N-dimethylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-diethylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-di-tert-butylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-trimethylsilylamino)phenyl]-1'-phenylethylene, 1-[4-(N,N-methyltrimethylsilylamino)phenyl]-1'-phenylethylene, and one or more amino-functionalized monomers selected from the following compounds: 1,1'-bis[4-(N,N-dimethyltrimethylsilylamino)phenyl]-1'-phenylethylene.

5. The type of star-shaped chain amino-functionalized high-impact polystyrene according to claim 1, characterized in that: The fSBC is selected from one or a mixture of several polymers selected from block butadiene / in-chain amino functionalized styrene copolymers, gradient block butadiene / in-chain amino functionalized styrene copolymers, and random block butadiene / in-chain amino functionalized styrene copolymers, or is a multi-block copolymer composed of several of the above polymers.

6. The method for preparing the star-shaped chain amino-functionalized high-impact polystyrene as described in claim 1, characterized in that: Includes the following steps: S1. Under nitrogen or argon protection, nonpolar hydrocarbon solvent, functional monomer activator, butadiene monomer, first batch of styrene monomer, and amino-functionalized DPE derivative are added to the reactor according to the specified ratio. A multifunctional alkyl lithium initiator is added for the first time. The reaction temperature is 30-70℃, and the reaction time is 1-5 hours to prepare C-(fSBC)n. The amount of multifunctional alkyl lithium initiator added for the first time is determined according to the number-average molecular weight of the fSBC single arm. The molar ratio of the functional monomer activator to the multifunctional alkyl lithium initiator is 1-100. S2. Add an optional anionic polymerization retarder, which is selected from one or more alkyl metal compounds and a mixture thereof. The molar ratio of the retarder to the multifunctional alkyl lithium initiator is 0.3-0.

9. S3. Add the second batch of styrene monomer and amino-functionalized DPE derivative to the reactor according to the ratio. Add the multifunctional alkyl lithium initiator for the second time. The amount of multifunctional alkyl lithium initiator added for the second time depends on the designed molecular weight of star-shaped polystyrene C-(fPS)n. The reaction temperature is 30-70℃ and the reaction time is 2-5 hours to prepare C-(fPS)n. At the same time, the C-(fSBC)n chain segment continues to grow to generate C-(fSBC-fPS)n.

7. The method according to claim 6, characterized in that: The multifunctional alkyl lithium initiator is selected from multifunctional alkyl lithium initiators that can be used in anionic polymerization systems, and can be one multifunctional alkyl lithium initiator or a mixture of several multifunctional alkyl lithium initiators.

8. The method according to claim 6, characterized in that: The aforementioned multifunctional alkyl lithium initiator RLin is a multichelate organic lithium initiator or a multifunctional alkyl lithium initiator; The anionic polymerization inhibitor is selected from one or a mixture of several alkyl aluminums selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tritert-butylaluminum, and tributylaluminum; The functional monomer activator used is selected from one or a mixture of several compounds, including oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and alkoxy metal compounds; The nonpolar hydrocarbon solvent is selected from one type of hydrocarbon solvent or a mixture of several types of hydrocarbon solvents, specifically nonpolar aromatic hydrocarbons and nonpolar aliphatic hydrocarbons.

9. The application of the star-shaped chain amine-functionalized high-impact polystyrene as described in claim 1 in the preparation of injection-molded articles and in the preparation of high-impact polystyrene blends.

10. The application according to claim 9, characterized in that: The injection-molded product is an electronic appliance housing, automotive interior parts, or a household appliance housing; the blend is composed of general-purpose polystyrene or high-impact polystyrene and 5–30 wt% of the star-shaped chain amine-functionalized high-impact polystyrene, and its Izod notched impact strength is ≥ 250 J / m.