1, 2-dihydronaphthalene derivative copolymer synthesized based on active anion polymerization and preparation method of 1, 2-dihydronaphthalene derivative copolymer

Abstract

A 1, 2-dihydronaphthalene derivative copolymer synthesized based on active anion polymerization and a preparation method thereof belong to the technical field of high polymer materials, are synthesized based on an active anion polymerization mechanism, and are formed by copolymerization of a 1, 2-dihydronaphthalene derivative, a styrene derivative and a diene monomer. The 1, 2-dihydronaphthalene derivative is 1, 2-dihydronaphthalene and functionalized 1, 2-dihydronaphthalene with a substituent group on an aromatic ring or an aliphatic ring; the styrene derivative is styrene, alpha-methyl styrene, 1, 1-diphenylethylene and a chain segment formed by mutual polymerization of the monomers; the dialkene monomer is butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and a chain segment formed by mutual polymerization of the dialkene monomer, the isoprene and the 2, 3-dimethyl-1, 3-butadiene. According to the invention, binary and ternary copolymerization of various monomers with similar structures but different performances is realized; the polymerization condition is mild, the copolymer with controllable molecular weight and distribution is easy to obtain, and the performance and application range of synthetic resin and synthetic rubber are further expanded.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a 1,2-dihydronaphthalene derivative copolymer based on active anion polymerization and a preparation method thereof. In particular, the present application relates to a 1,2-dihydronaphthalene derivative copolymer based on active anion polymerization, which realizes binary copolymerization of 1,2-dihydronaphthalene derivative and diene monomer and ternary copolymerization of 1,2-dihydronaphthalene derivative, styrene derivative and diene monomer. BACKGROUND

[0002] 1,2-dihydronaphthalene (1,2-DHN) can be regarded as a fused ring analogue of styrene in structure. It not only retains the core characteristics of styrene: an active vinyl group is connected to an aromatic system, and its double bond is located in a six-membered ring, so that the rigidity of the polymer formed by polymerization is greatly improved, and therefore it is very significant to study. Copolymer of styrene derivative and diene monomer is an important basis in the field of high polymer materials, and styrene-butadiene block copolymer (SBS) is widely used in automobile industry, electronic technology, medical supplies, aerospace and other fields due to its excellent elastic properties. With the continuous improvement of the demand for performance diversification in material science, it is of great significance to explore new monomers and their copolymers with similar structure but possibly different properties. At present, the use of general synthetic resins and synthetic rubbers is limited by their use temperature (Tg). The present application uses styrene fused ring analogue 1,2-dihydronaphthalene to copolymerize with diene monomer and styrene derivative to form a new synthetic resin to expand its application range.

[0003] Active anion polymerization (LAP) has the characteristics of no termination and no chain transfer, and its active chain end has continuous growth ability, which can realize precise control of molecular weight and molecular structure, and is a classic preparation method of synthetic resin and synthetic rubber. Therefore, by using the unique controllable ability of active center of active anion polymerization and its ability to generate narrow distribution molecular chain, a new type of 1,2-dihydronaphthalene derivative copolymer with mild reaction conditions and narrow molecular chain distribution and a preparation method thereof are developed, which is the innovation of the present application. SUMMARY

[0004] The purpose of the present application is to break through the traditional synthesis of styrene derivatives and diene monomers, and to propose a kind of 1, 2-dihydronaphthalene derivative copolymer synthesized by introducing new styrene fused ring derivatives and its preparation method. First, based on the active anion polymerization method, 1, 2-dihydronaphthalene and diene monomers are solution polymerized at a suitable temperature to obtain a binary copolymer with controllable molecular weight and distribution. On this basis, styrene or its derivatives are added to the polymerization system. Due to the electron-withdrawing effect of the conjugated system in the monomers in the system, the monomers are easily attacked by the anion active center, and a ternary copolymer of 1, 2-dihydronaphthalene derivative, styrene derivative and diene monomer is obtained.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A kind of 1, 2-dihydronaphthalene derivative copolymer synthesized based on active anion polymerization method, the 1, 2-dihydronaphthalene derivative copolymer is composed of 1, 2-dihydronaphthalene derivative, styrene derivative and diene monomer copolymerization;The 1, 2-dihydronaphthalene derivative is 1, 2-dihydronaphthalene and functionalized 1, 2-dihydronaphthalene with substituent group on the aromatic ring or aliphatic ring, wherein the functional group includes one or more of hydrocarbon group, nitrogen atom group, siloxane group, hydroxyl group, silicon hydrogen group, alkyne group, mercapto group, fluorine atom group, chlorine atom group and bromine atom group. The styrene derivative is styrene, α-methylstyrene, 1, 1-diphenyl ethylene (DPE) and the segment composed of mutual polymerization of these monomers. The diene monomer is butadiene (BP), isoprene (Ip), 2, 3-dimethyl-1, 3-butadiene (DMBD) and the segment composed of mutual polymerization of these monomers. Specifically:

[0007] The proportion of each component in the binary and ternary copolymer of 1, 2-dihydronaphthalene derivative, styrene derivative and diene monomer is 1% to 99% (molar fraction mol%) of the total amount of the product, the styrene derivative part accounts for 0% to 98% of the total amount of the product, and the diene monomer part accounts for 1% to 99% of the total amount of the product. The number average molecular weight of the binary and ternary copolymer of 1, 2-dihydronaphthalene derivative, styrene derivative and diene monomer in this series is generally in the range of 2-100×10 3 kg / mol.

[0008] The total of 42 kinds of binary and ternary copolymers of the 1,2-dihydronaphthalene derivative and styrene derivatives and diene monomers are as follows: No. 1: 1,2-DHN-co-Ip binary copolymer; No. 2: 1,2-DHN-co-BP binary copolymer; No. 3: 1,2-DHN-co-DMBD binary copolymer; No. 4: 1,2-DHN-co-Ip-co-BP ternary copolymer; No. 5: 1,2-DHN-co-Ip-co-DMBD ternary copolymer; No. 6: 1,2-DHN-co-BP-co-DMBD ternary copolymer; No. 7: 1,2-DHN-co-Ip-co-St ternary copolymer; No. 8: 1,2-DHN-co-Ip-co-AMS ternary copolymer; No. 9: 1,2-DHN-co-Ip-co-DPE ternary copolymer; No. 10: 1,2-DHN-co-BP-co-DPE ternary copolymer; No. 11: 1,2-DHN-co-DMBD-co-DPE ternary copolymer; No. 12: 1,2-DHN-co-BP-co-St ternary copolymer; No. 13: 1,2-DHN-co-BP-co-AMS ternary copolymer; No. 14: 1,2-DHN-co-DMBD-co-AMS ternary copolymer; No. 15: 1,2-DHN-co-DMBD-co-St ternary copolymer; No. 16: 1,2-DHN-alt-Ip binary alternating copolymer; No. 17: 1,2-DHN-alt-BP binary alternating copolymer; No. 18: 1,2-DHN-alt-DMBD binary alternating copolymer; No. 19: 1,2-DHN-block-BP binary block copolymer; No. 20: 1,2-DHN-block-Ip binary block copolymer; No. 21: 1,2-DHN-block-DMBD binary block copolymer; No. 22: 1,2-DHN-block-DMBD-block-1,2-DHN binary block copolymer; No. 23: 1,2-DHN-block-Ip-block-1,2-DHN binary block copolymer; No. 24: 1,2-DHN-block-BP-block-1,2-DHN binary block copolymer; No. 25: 1,2-DHN-block-Ip / St ternary block copolymer; No. 26: 1,2-DHN-block-Ip / AMS ternary block copolymer; No. 27: 1,2-DHN-block-Ip / DPE ternary copolymer; No. 28: 1,2-DHN-block-BP / DPE ternary copolymer; No. 29: 1,2-DHN-block-BP / AMS ternary block copolymer; No. 30: 1,2-DHN-block-BP / St ternary block copolymer; No. 31: 1,2-DHN-block-DMBD / AMS ternary block copolymer;32: 1,2-DHN-block-DMBD / DPE terpolymer; 33: 1,2-DHN-block-DMBD / St terpolymer; 34: 1,2-DHN-block-Ip-block-St terpolymer; 35: 1,2-DHN-block-Ip-block-AMS terpolymer; 36: 1,2-DHN-block-Ip-block-DPE terpolymer; 37: 1,2-DHN-block-BP-block-DPE terpolymer; 38: 1,2-DHN-block-BP-block-AMS terpolymer; 39: 1,2-DHN-block-BP-block-St terpolymer; 40: 1,2-DHN-block-DMBD-block-AMS terpolymer; 41: 1,2-DHN-block-DMBD-block-DPE terpolymer; 42: 1,2-DHN-block-DMBD-block-St terpolymer;

[0009] The Ip / AMS, Ip / St, Ip / DPE, BP / DPE, BP / St, BP / AMS, DMBD / AMS, DMBD / St, DMBD / DPE respectively represent Ip and AMS copolymer, Ip and St copolymer, Ip and DPE copolymer, BP and DPE copolymer, BP and St copolymer, BP and DPE copolymer, DMBD and AMS copolymer, DMBD and BP copolymer, DMBD and Ip copolymer, and the copolymer composition includes random, alternating, gradient, block sequence structure.

[0010] Further, the dihydronaphthalene derivative, styrene derivative and diene monomer can be further expanded and functionalized. For example, the DPE monomer can be one or more of the following functionalized monomers: nitrogen atom-containing group, siloxyl group, hydroxyl group, silicon hydrogen group, alkyne group, mercapto group, fluorine atom group, chlorine atom group, bromine atom group.

[0011] A preparation method of a 1,2-dihydronaphthalene derivative copolymer based on active anion polymerization synthesis, comprising the following steps:

[0012] S1, under the protection of nitrogen or argon, a 1,2-dihydronaphthalene monomer is added to a polymerization reactor, and then an organic solvent and a polarity regulator (polarity additive / initiator = 0-100 equivalents) are sequentially added, the reaction liquid in the polymerization reactor is heated or cooled to a polymerization temperature of -50°C-80°C, an initiator is added, and the reaction is carried out for 0.5-36h.

[0013] S2, under the protection of nitrogen or argon, one or more of diene monomer and styrene monomer is added into the polymerization reaction solution, and the reaction is continued at -50-80°C for 3-72h.

[0014] S3, under the protection of nitrogen or argon, isopropanol is injected into the reaction solution to terminate the polymerization, the gel is precipitated, and dried to constant weight in a vacuum drying oven.

[0015] Further, after the S3 polymerization reaction is completed, the polymer gel is treated by a conventional method, and the product structure and performance are analyzed after drying.

[0016] Further, in the S1, when the block copolymers No. 22-24 are synthesized, the initiator is a bifunctional initiator; when the 1,2-dihydronaphthalene derivative copolymers No. 1-21 and No. 25-42 are synthesized, the initiator is a monofunctional initiator; preferably, the monofunctional initiator is selected from any initiator or mixture of initiators disclosed in the prior art that can be used in anionic polymerization, and is generally selected from one or a mixture of several monofunctional lithium initiators selected from RLi and TRLi, R is a hydrocarbon group with a carbon atom number of 2-20, R can be an alkyl group or an aromatic hydrocarbon group, T is a metal atom or a nitrogen atom, and is generally a metal element such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge, etc., and is preferably selected from ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, monofunctional lithium initiators containing tin or nitrogen atoms, etc.

[0017] Preferably, the bifunctional initiator is any initiator or mixture of initiators disclosed in the prior art that can be used in anionic polymerization, and is generally selected from naphthalene sodium, naphthalene lithium, naphthalene potassium, or 1,3-bis(1-phenylvinyl)benzene (MDDPE) initiated by monofunctional alkyl lithium.

[0018] Further, in the S1, the organic solvent is selected from one or a mixture of several hydrocarbon solvents selected from non-polar aromatic hydrocarbons and non-polar aliphatic hydrocarbons, and is generally selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, n-hexane, cyclopentane, mixed aromatic hydrocarbons (such as mixed xylene), mixed aliphatic hydrocarbons (such as raffinate oil), and one or a mixture of several thereof, and is preferably selected from benzene, toluene, hexane, n-hexane, cyclohexane, cyclopentane, and one or a mixture of several thereof.

[0019] Further, the S1, the polar additive is selected from one or several compounds of 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 (THF), R1OCH2CH2OR2(wherein: R1, R2 are alkyl groups with carbon atom number of 1-6, R1, R2 can be the same or different, preferably R1, R2 are different, such as: ethylene glycol dimethyl ether, ethylene glycol diethyl ether), R1OCH2CH2OCH2CH2OR2(wherein: R1, R2 are alkyl groups with carbon atom number of 1-6, R1, R2 can be the same or different, preferably R1, R2 are different, such as: diethylene glycol dimethyl ether, diethylene glycol dibutyl ether), crown ether; (2) nitrogen-containing compounds, generally selected from: triethylamine, tetramethyl ethylenediamine (TMEDA), dipiperidine ethane; (3) phosphorus-containing compounds, generally selected from hexamethyl phosphoric triamide (HMPA); (4) alkoxy metal compounds generally selected from ROM, wherein: R is an alkyl group with carbon atom number of 1-6, O is an oxygen atom, M is a metal sodium Na or potassium K, preferably selected from: tert-butoxy potassium, tert-pentyl potassium, 2,3-dimethyl-3-pentanol sodium (NaODP).

[0020] The present application has the following beneficial effects:

[0021] Since 1,2-dihydronaphthalene is a fused ring analogue of styrene, it has high rigidity while retaining the polymerization characteristics of styrene. The present application is based on the mechanism of living anionic polymerization, and by copolymerizing 1,2-dihydronaphthalene derivatives, styrene derivatives and diene monomers, a binary and ternary copolymer is synthesized, providing a kind of 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization and a preparation method thereof. The method realizes binary copolymerization of 1,2-dihydronaphthalene and diene monomers, ternary copolymerization of 1,2-dihydronaphthalene, styrene derivatives and diene monomers, and precise control of molecular weight, distribution and composition. Moreover, the polymerization conditions of the method are mild, the composition of the copolymer can be simply controlled by the amount of charge, the operation is convenient, the applicability is wide, further invention of the synthetic resin and synthetic rubber species synthesized from new monomers expands the performance and application range of synthetic resin and synthetic rubber. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 Synthesis route of 1,2-dihydronaphthalene derivative copolymer;

[0023] Figure 2 NMR hydrogen spectrum of Ip-1,2-DHN binary random polymer (Example 1, No. 1). DETAILED DESCRIPTION

[0024] The following examples are presented as further illustration of the application, but are not intended to limit the scope of the claims. The composition sequence distribution and microstructure of the block polymers were analyzed by nuclear magnetic resonance spectrometer, infrared spectrometer and time-of-flight mass spectrometer. The molecular weight and molecular weight distribution index (weight average molecular weight to number average molecular weight ratio) of the block polymers were analyzed by gel permeation chromatograph.

[0025] Example 1 (No. 1)

[0026] Under nitrogen or argon protection, 1,2-dihydronaphthalene monomer 9.0 g, 3.7 g Ip and 120 mL solvent THF were sequentially added into a polymerization reactor, stirred uniformly and the reaction solution was cooled to polymerization temperature -50°C, then initiator sec-butyllithium was added according to the designed molecular weight 2 kg / mol. The reaction was kept at -50°C for 12 h. Degassed isopropyl alcohol was added to terminate the polymerization, the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a binary random copolymer; the number average molecular weight is 2.1 kg / mol, the molecular weight distribution is 1.07; the dihydronaphthalene segment accounts for 44% in terms of molar percentage; the glass transition temperature (T g ) is 88°C. In addition, from the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peak of 1,2-dihydronaphthalene appears at chemical shift 6.3-7.6 ppm, and the diene double bond hydrogen peak representing different addition modes appears at chemical shift 5.4-5.8 ppm and 4.1-5.3 ppm, confirming the successful synthesis of Ip-1,2-dihydronaphthalene copolymer. Figure 2

[0027] Example 2 (No. 4)

[0028] Under nitrogen or argon protection, 1,2-dihydronaphthalene monomer 4.0 g, 1.5 g Ip, 1 g BP and 120 mL solvent toluene were sequentially added into a polymerization reactor, stirred uniformly and the reaction solution was cooled to polymerization temperature 80°C, then initiator sec-butyllithium and polarity modifier THF (polar additive / initiator = 15 equivalents) were added according to the designed molecular weight 20 kg / mol. The reaction was kept at 0°C for 24 h. Degassed isopropyl alcohol was added to terminate the polymerization, the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a ternary random copolymer; the number average molecular weight is 21 kg / mol, the molecular weight distribution is 1.18; the dihydronaphthalene segment accounts for 24%; the glass transition temperature (T g ) is 15°C. In the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peak of 1,2-dihydronaphthalene appears at chemical shift 6.0-7.4 ppm, and the diene double bond hydrogen peak representing different addition modes appears at chemical shift 4.2-5.5 ppm. ​

[0029] Example 3 (No. 7)

[0030] Under nitrogen or argon protection, 1,2-dihydronaphthalene monomer 6.0 g, 3 g Ip, 5 g St and 120 mL solvent toluene were added into the polymerization reactor in turn, stirred uniformly and the reaction solution was cooled to the polymerization temperature -20 °C, then initiator n-butyllithium and polarity modifier THF (polar additive / initiator = 20 eq) were added according to the designed molecular weight 20 kg / mol. The reaction was kept at -20 °C for 3 h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a ternary random copolymer; the number average molecular weight is 22 kg / mol, the molecular weight distribution is 1.18; the dihydronaphthalene segment accounts for 22%; the glass transition temperature (T g ) is 79 °C. In the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peaks of 1,2-dihydronaphthalene and styrene appear at chemical shift 5.7-7.1 ppm, and the diene double bond hydrogen peaks representing different addition modes appear at chemical shift 4.1-5.6 ppm.

[0031] Example 4 (No. 16)

[0032] Under nitrogen or argon protection, 1,2-dihydronaphthalene monomer 6.0 g and 120 mL solvent benzene were added into the polymerization reactor in turn, stirred uniformly and the reaction solution was heated to the polymerization temperature -40 °C, then initiator n-butyllithium and polarity modifier THF (polar additive / initiator = 0 eq) were added according to the designed molecular weight 20 kg / mol. After the system reacted for 0.5 h, 4 g Ip was added into the polymerization reaction solution, and the reaction was continued at -40 °C for 30 h. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a binary alternating polymer; the number average molecular weight is 25 kg / mol, the molecular weight distribution is 1.14; the dihydronaphthalene segment accounts for 48%; the glass transition temperature (T g ) is 85 °C. In the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peaks of 1,2-dihydronaphthalene appear at chemical shift 6.1-8.1 ppm, and the diene double bond hydrogen peaks representing different addition modes appear at chemical shift 4.3-5.3 ppm.

[0033] Example 5 (No. 20)

[0034] Under nitrogen or argon protection, 1,2-dihydronaphthalene monomer 6.0 g and 120 mL solvent benzene were added into a polymerization reactor in turn, stirred uniformly and the reaction liquid was warmed to polymerization temperature 30°C, then initiator n-butyllithium and polar modifier THF (polar additive / initiator = 15 eq) were added according to the designed molecular weight 20 kg / mol. After the system reacted for 30 h, 4 g Ip was added into the polymerization reaction liquid, and the reaction was continued at 30°C for 72 h. The polymerization was terminated by adding degassed isopropanol, and the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a block polymer; the number average molecular weight is 26 kg / mol, and the molecular weight distribution is 1.12; the dihydronaphthalene chain segment accounts for 48%; the block polymer has double glass transition temperatures, the main T g is 124°C, and the secondary T g is -35°C. In the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peak of 1,2-dihydronaphthalene appears at a chemical shift of 5.7-7.1 ppm, and the diene double bond hydrogen peak representing different addition modes appears at a chemical shift of 4.1-5.6 ppm.

[0035] Example 6 (No. 23)

[0036] Under nitrogen or argon protection, 12 g Ip and 120 mL solvent toluene were added into a polymerization reactor in turn, stirred uniformly and the reaction liquid was warmed to polymerization temperature 20°C, then initiator naphthalene sodium and polar modifier TMEDA (polar additive / initiator = 10 eq) were added according to the designed molecular weight 40 kg / mol. After the system reacted for 48 h, 1,2-dihydronaphthalene monomer 10.0 g was added into the polymerization reaction liquid, and the reaction was continued at 20°C for 48 h. The polymerization was terminated by adding degassed isopropanol, and the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a block polymer; the number average molecular weight is 43 kg / mol, and the molecular weight distribution is 1.13; the dihydronaphthalene chain segment accounts for 28%; the block polymer has double glass transition temperatures, the main T g is 66°C, and the secondary T g is 22°C. In the nuclear magnetic resonance hydrogen spectrum, the benzene ring hydrogen peak of 1,2-dihydronaphthalene appears at a chemical shift of 5.6-7.1 ppm, and the diene double bond hydrogen peak representing different addition modes appears at a chemical shift of 4.0-5.2 ppm.

[0037] Example 7 (No. 25)

[0038] Under the protection of nitrogen or argon, 1,2-dihydronaphthalene monomer 5.0 g and 120 mL solvent toluene were sequentially added into a polymerization reactor, stirred uniformly and the reaction solution was cooled to the polymerization temperature 60 °C, then initiator n-butyllithium and polar modifier THF (polar additive / initiator = 10 equivalents) were added according to the designed molecular weight 20 kg / mol. After the system reacted for 48 h, 3.0 g Ip and 4.0 g St were added into the polymerization reaction solution, and the reaction was continued at 60 °C for 3 h. The polymerization was terminated by adding degassed isopropanol, and the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a block polymer; the number average molecular weight is 21 kg / mol, and the molecular weight distribution is 1.15; the proportion of 1,2-dihydronaphthalene segment is 32%; the block polymer has a wide glass transition temperature, Tg g The hydrogen peaks of the benzene ring of 1,2-dihydronaphthalene and styrene appeared at the chemical shift of 5.6-8.0 ppm in the hydrogen nuclear magnetic resonance spectrum, and the hydrogen peaks of the double bond of the diene representing different addition modes appeared at the chemical shift of 4.3-5.3 ppm.

[0039] Example 8 (No. 34)

[0040] Under the protection of nitrogen or argon, 1,2-dihydronaphthalene monomer 5.0 g and 120 mL solvent toluene were sequentially added into a polymerization reactor, stirred uniformly and the reaction solution was cooled to the polymerization temperature 60 °C, then initiator n-butyllithium and polar modifier THF (polar additive / initiator = 10 equivalents) were added according to the designed molecular weight 20 kg / mol. After the system reacted for 48 h, 3.0 g Ip and 4.0 g St were added into the polymerization reaction solution, and the reaction was continued at 60 °C for 3 h. The polymerization was terminated by adding degassed isopropanol, and the reaction solution was precipitated in excess anhydrous ethanol, and the obtained polymer was dried to constant weight in a vacuum oven. The product structure analysis results are as follows: the polymer is a block polymer; the number average molecular weight is 21 kg / mol, and the molecular weight distribution is 1.15; the proportion of 1,2-dihydronaphthalene segment is 32%; the block polymer has a wide glass transition temperature, Tg g The hydrogen peaks of the benzene ring of 1,2-dihydronaphthalene and styrene appeared at the chemical shift of 5.6-8.0 ppm in the hydrogen nuclear magnetic resonance spectrum, and the hydrogen peaks of the double bond of the diene representing different addition modes appeared at the chemical shift of 4.3-5.3 ppm.

[0041] The above examples only express the embodiments of the present application, but cannot be understood as the limitation of the scope of the present application patent. It should be pointed out that for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application.

Claims

1. A class of 1,2-dihydronaphthalene derivative copolymers synthesized by living anionic polymerization, characterized in that, The 1,2-dihydronaphthalene derivative copolymer is composed of 1,2-dihydronaphthalene derivatives, styrene derivatives, and diene monomers copolymerized together, including binary or ternary copolymers of 1,2-dihydronaphthalene derivatives, styrene derivatives, and diene monomers; the 1,2-dihydronaphthalene derivatives are 1,2-dihydronaphthalene and functionalized 1,2-dihydronaphthalene with substituents on the aromatic or aliphatic rings; the styrene derivatives are styrene, α-methylstyrene, 1,1-diphenylethylene (DPE), and segments polymerized from these monomers; the diene monomers are butadiene (BP), isoprene (Ip), 2,3-dimethyl-1,3-butadiene (DMBD), and segments polymerized from these monomers.

2. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 1, characterized in that, In the 1,2-dihydronaphthalene derivatives, the functional groups in the functionalized 1,2-dihydronaphthalene include one or more of the following: hydrocarbon groups, nitrogen groups, siloxy groups, hydroxyl groups, silane groups, alkynyl groups, mercapto groups, fluorine groups, chlorine groups, and bromine groups.

3. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 1, characterized in that, The proportions of each component in the binary or ternary copolymer of the 1,2-dihydronaphthalene derivative, styrene derivative, and diene monomer are based on 100% of the total 1,2-dihydronaphthalene derivative copolymer product. The 1,2-dihydronaphthalene derivative portion accounts for 1%-99% of the total molar fraction, the styrene derivative portion accounts for 0%-98% of the total molar fraction, and the diene monomer portion accounts for 1%-99% of the total molar fraction.

4. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 1, characterized in that, The number-average molecular weight range of the binary or ternary copolymers of the 1,2-dihydronaphthalene derivative with styrene derivatives and diene monomers is 2-100 × 10⁻⁶. 3 kg / mol.

5. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 1, characterized in that, A total of 42 binary and ternary copolymers of the 1,2-dihydronaphthalene derivatives with styrene derivatives and diene monomers are specified as follows: No. 1: 1,2-DHN-co-Ip binary copolymer; No. 2: 1,2-DHN-co-BP binary copolymer; No. 3: 1,2-DHN-co-DMBD binary copolymer; No. 4: 1,2-DHN-co-Ip-co-BP ternary copolymer; No. 5: 1,2-DHN-co-Ip-co-DMBD ternary copolymer; No. 6: 1,2-DHN-co-BP-co-DMBD ternary copolymer; No. 7: 1,2-DHN-co-Ip-co-St ternary copolymer; No. 8: 1,2-DHN-co-I... p-co-AMS terpolymer; No. 9: 1,2-DHN-co-Ip-co-DPE terpolymer; No. 10: 1,2-DHN-co-BP-co-DPE terpolymer; No. 11: 1,2-DHN-co-DMBD-co-DPE terpolymer; No. 12: 1,2-DHN-co-BP-co-St terpolymer; No. 13: 1,2-DHN-co-BP-co-AMS terpolymer; No. 14: 1,2-DHN-co-DMBD-co-AMS terpolymer; No. 15: 1,2-DHN-co-DMBD-co-St terpolymer; No. 16: 1,2-DHN-alt-Ip binary copolymer Alternating copolymers; No. 17: 1,2-DHN-alt-BP binary alternating copolymer; No. 18: 1,2-DHN-alt-DMBD binary alternating copolymer; No. 19: 1,2-DHN-block-BP binary block copolymer; No. 20: 1,2-DHN-block-Ip binary block copolymer; No. 21: 1,2-DHN-block-DMBD binary block copolymer; No. 22: 1,2-DHN-block-DMBD-block-1,2-DHN binary block copolymer; No. 23: 1,2-DHN-block-Ip-block-1,2-DHN binary block copolymer; No. 24: 1,2-DHN-block-BP binary block copolymer; ck-BP-block-1,2-DHN binary block copolymer; No. 25: 1,2-DHN-block-Ip / St ternary block copolymer; No. 26: 1,2-DHN-block-Ip / AMS ternary block copolymer; No. 27: 1,2-DHN-block-Ip / DPE ternary copolymer; No. 28: 1,2-DHN-block-BP / DPE ternary copolymer; No. 29: 1,2-DHN-block-BP / AMS ternary block copolymer; No. 30: 1,2-DHN-block-BP / St ternary block copolymer; No. 31: 1,2-DHN-block-DMBD / AMS ternary block copolymer;No. 32: 1,2-DHN-block-DMBD / DPE terpolymer; No. 33: 1,2-DHN-block-DMBD / St terblock copolymer; No. 34: 1,2-DHN-block-Ip-block-St terblock copolymer; No. 35: 1,2-DHN-block-Ip-block-AMS terblock copolymer; No. 36: 1,2-DHN-block-Ip-block-DPE terpolymer; No. 37: 1,2-DHN-block-BP-block -DPE terpolymer; No. 38: 1,2-DHN-block-BP-block-AMS terblock copolymer; No. 39: 1,2-DHN-block-BP-block-St terblock copolymer; No. 40: 1,2-DHN-block-DMBD-block-AMS terblock copolymer; No. 41: 1,2-DHN-block-DMBD-block-DPE terpolymer; No. 42: 1,2-DHN-block-DMBD-block-St terblock copolymer.

6. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 5, characterized in that, The Ip / AMS, Ip / St, Ip / DPE, BP / DPE, BP / St, BP / AMS, DMBD / AMS, DMBD / St, and DMBD / DPE respectively represent Ip and AMS copolymer, Ip and St copolymer, Ip and DPE copolymer, BP and DPE copolymer, BP and St copolymer, BP and DPE copolymer, DMBD and AMS copolymer, DMBD and BP copolymer, and DMBD and Ip copolymer. The copolymer composition includes random, alternating, gradient, and block sequence structures.

7. The 1,2-dihydronaphthalene derivative copolymer synthesized based on living anionic polymerization according to claim 1, characterized in that, The dihydronaphthalene derivatives, styrene derivatives, and diene monomers can be further expanded and functionalized; taking DPE as an example, DPE monomers can also be one or more functionalized monomers selected from the substituents containing nitrogen atoms, siloxy groups, hydroxy groups, silane groups, alkynyl groups, mercapto groups, fluorine groups, chlorine groups, and bromine groups.

8. A method for preparing a 1,2-dihydronaphthalene derivative copolymer based on living anionic polymerization as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Under nitrogen or argon protection, add 1,2-dihydronaphthalene monomer to the polymerization reactor, followed by organic solvent and polarity modifier in sequence. Heat or cool the reaction liquid in the polymerization reactor to the polymerization temperature of -50℃ to 80℃, add initiator, and react for 0.5-36 hours. When synthesizing block copolymers No. 22-24, the initiator is a bifunctional initiator; when synthesizing 1-21 and 25-42 1,2-dihydronaphthalene derivative copolymers, the initiator is a monofunctional initiator. S2. Under nitrogen or argon protection, add one or more diene monomers and styrene monomers to the polymerization reaction solution, and continue the reaction at -50℃ to 80℃ for 3-72 hours. S3. Under nitrogen or argon protection, inject isopropanol into the reaction solution to terminate the polymerization, precipitate the gel, and dry it to constant weight in a vacuum drying oven.

9. The method for preparing a type of 1,2-dihydronaphthalene derivative copolymer based on living anionic polymerization according to claim 8, characterized in that, In S1: The monofunctional initiator is selected from monofunctional alkyl lithium initiators; The aforementioned bifunctional initiator is any initiator or mixture of several initiators that can be used in anionic polymerization reactions; The organic solvent is selected from one type of hydrocarbon solvent or a mixture of several types of hydrocarbon solvents, including nonpolar aromatic hydrocarbons and nonpolar aliphatic hydrocarbons. The polar additive 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.

10. The method for preparing a type of 1,2-dihydronaphthalene derivative copolymer based on living anionic polymerization according to claim 9, characterized in that, The preferred polar additives are potassium tert-butoxy, potassium tert-pentoxy, and sodium 2,3-dimethyl-3-pentanol.

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