Liquid styrene-butadiene polymer, preparation method and application thereof, composition and application thereof, polymer coating, adhesive and crosslinking agent

Abstract

The present invention relates to the field of polymers, and discloses a liquid styrene butadiene polymer and its preparation method and application, composition and application, polymer coating, adhesive and cross-linking agent. The liquid styrene butadiene polymer has the following characteristics: based on the total weight of butadiene in the liquid styrene butadiene polymer, the 1,2-structure content is 80-90 weight%; the styrene content is 15-30 weight%, and the styrene block content is 0.1-0.5 weight%; the number average molecular weight of the liquid styrene butadiene polymer is 1500-4500; the molecular weight distribution is 1.2-1.6; and the dynamic viscosity at 45°C is 100-500P. The liquid styrene butadiene polymer has a high vinyl content, a suitable molecular weight distribution, a number average molecular weight and a dynamic viscosity, thereby making the polymer have good flow properties, film-forming properties and coating properties. When used in a polymer coating, it can significantly improve the mechanical properties and glass transition temperature of the polymer coating.

Description

Technical Field

[0001] The present invention relates to the field of polymers, and in particular to a liquid styrene-butadiene polymer and a preparation method and application thereof, a composition and application thereof, a polymer coating, an adhesive and a crosslinking agent. Background Art

[0002] Liquid styrene butadiene polymer is a viscous flowable polymer with a number average molecular weight of 500-10,000. It is widely used in resin modifiers, plasticizers, additives, photographic materials, adhesives, water-based coatings, electrophoretic coatings, electrical insulation materials, sintering adhesives, etc.

[0003] According to the microstructure classification, liquid styrene butadiene polymer can be divided into random liquid styrene butadiene polymer and block liquid styrene butadiene polymer.

[0004] Liquid styrene butadiene polymers are typically produced using anionic solution polymerization, but molecular weight regulation is heavily dependent on catalyst dosage. The production of low-molecular-weight liquid styrene butadiene polymers via anionic solution polymerization often results in high catalyst dosages and difficulty in catalyst removal. Furthermore, the ability of the structure modifiers used in anionic polymerization to regulate the polymer microstructure is highly sensitive to temperature, making it challenging to achieve stable and controllable microstructures. However, the 1,2-unit content, styrene unit content, molecular weight, and their distribution significantly influence the properties of liquid styrene butadiene polymers.

[0005] Liquid styrene butadiene polymer has the characteristics of low dielectric constant and low dielectric loss, and has good application prospects in the field of communication technology. However, the development of modern communication technology has put forward higher requirements for communication materials. Therefore, it is of great significance to solve the technical problems existing in the preparation process of liquid styrene butadiene polymer and obtain liquid styrene butadiene polymer with better performance to meet the rapid development of communication technology. Summary of the Invention

[0006] The present invention aims to overcome the technical problem of difficulty in stably controlling the microstructure of liquid styrene butadiene polymer solution polymerization processes in the prior art, and to provide a liquid styrene butadiene polymer, a preparation method and application thereof, a composition and application thereof, a polymer coating, an adhesive, and a crosslinking agent. The liquid styrene butadiene polymer has a high vinyl content and a moderate molecular weight distribution, as well as an appropriate molecular weight and dynamic viscosity. This results in the liquid styrene butadiene polymer having good flow properties, film-forming properties, and coating properties. When used to form a polymer coating, the polymer coating can significantly improve its mechanical properties and heat resistance.

[0007] In order to achieve the above object, the first aspect of the present invention provides a liquid styrene butadiene polymer, characterized in that the liquid styrene butadiene polymer has the following characteristics:

[0008] (1) Based on the total weight of butadiene in the liquid styrene butadiene polymer, the 1,2-structure content of the liquid styrene butadiene polymer is 80-90% by weight;

[0009] (2) based on the total weight of the liquid styrene butadiene polymer, the styrene content in the liquid styrene butadiene polymer is 15-30% by weight, and the styrene block content is 0.1-0.5% by weight;

[0010] (3) the number average molecular weight of the liquid styrene-butadiene polymer is 1500-4500;

[0011] (4) the molecular weight distribution of the liquid styrene-butadiene polymer is 1.2-1.6;

[0012] (5) The dynamic viscosity of the liquid styrene-butadiene rubber at 45° C. is 100-500P.

[0013] A second aspect of the present invention provides a method for preparing a liquid styrene-butadiene polymer, characterized in that the method comprises:

[0014] Under anionic polymerization conditions, 1,3-butadiene monomer, styrene monomer, 1,2-butadiene monomer, a structure regulator and an organic lithium initiator are contacted and reacted in a polymerization solvent to obtain the liquid styrene-butadiene polymer;

[0015] The temperature of the contact reaction is below 20°C;

[0016] The structure regulator comprises component A and component B; component A is selected from ether compounds and / or amine compounds; component B is an alkali metal alkoxide;

[0017] The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-12:1000;

[0018] The weight ratio of the 1,3-butadiene monomer to the styrene monomer is 2.3-5.7:1;

[0019] The molar ratio of the organic lithium initiator, the component A and the component B is 1:0.05-0.3:0.03-0.2, and the organic lithium initiator is calculated as lithium;

[0020] The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 1500-4500.

[0021] The third aspect of the present invention provides a liquid styrene-butadiene polymer prepared by the above preparation method.

[0022] A fourth aspect of the present invention provides a composition, characterized in that the composition contains a liquid styrene butadiene polymer and at least one additive, and the liquid styrene butadiene polymer is the above-mentioned liquid styrene butadiene polymer.

[0023] A fifth aspect of the present invention provides a polymer coating, characterized in that the polymer coating contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0024] A sixth aspect of the present invention provides an adhesive, characterized in that the adhesive contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0025] A seventh aspect of the present invention provides a cross-linking agent, characterized in that the cross-linking agent contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0026] An eighth aspect of the present invention provides the use of the liquid styrene-butadiene polymer or the composition as a cross-linking agent, adhesive or electrical insulating material.

[0027] Through the above technical solution, the liquid styrene-butadiene polymer provided by the present invention, its preparation method and application, composition and application, polymer coating, adhesive and crosslinking agent achieve the following beneficial effects:

[0028] The liquid styrene butadiene polymer provided by the present invention not only has a high vinyl content, but also has a moderate molecular weight distribution, and simultaneously has a suitable molecular weight and dynamic viscosity, thereby enabling the liquid styrene butadiene polymer to have good flowability, film-forming property and coating property, and is particularly suitable for forming a polymer coating.

[0029] Furthermore, the polymer coating formed from the liquid styrene-butadiene polymer provided by the present invention has improved adhesion to the substrate and glass transition temperature.

[0030] Furthermore, the liquid styrene-butadiene polymer provided by the present invention has good application prospects in the fields of crosslinking agents, adhesives, electrical insulation materials and communication technology. DETAILED DESCRIPTION

[0031] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0032] In the present invention, the term "liquid styrene butadiene polymer" refers to a styrene butadiene polymer having fluidity at 25°C and 1 standard atmospheric pressure.

[0033] In the present invention, the term "styrene structural unit" refers to a structural unit formed by the polymerization of styrene monomers, and the term "butadiene structural unit" refers to a structural unit formed by the polymerization of butadiene monomers. In the present invention, the content of styrene structural units and butadiene structural units in the polymer is determined by nuclear magnetic resonance spectroscopy.

[0034] In the present invention, the term "1,2-structural unit" refers to a structural unit formed by 1,3-butadiene polymerization. The content of 1,2-structural units may also be referred to as vinyl content. In the present invention, the content of 1,2-structural units in the polymer is determined by nuclear magnetic resonance spectroscopy.

[0035] In the present invention, the term "styrene block" means that the structural units in the block are all derived from styrene, and the number of structural units in the block is greater than 5. In the present invention, the content of styrene block in the polymer is determined by nuclear magnetic resonance spectroscopy.

[0036] In the present invention, the specific testing method of nuclear magnetic resonance spectroscopy is: using a Bruker AVANCE400 superconducting nuclear magnetic resonance wave instrument ( 1 H-NMR) test, 1 The resonance frequency of the H nucleus is 300.13 MHz, the spectral width is 2747.253 Hz, the pulse width is 5.0 μs, the data point is 16 K, the sample tube diameter is 5 mm, the solvent is deuterated chloroform (CDCl3), the sample concentration is 15% (mg / mL), the test temperature is room temperature (25°C), the number of scans is 16 times, and the calibration is based on the tetramethylsilane chemical shift of 0 ppm.

[0037] In the present invention, molecular weight and molecular weight distribution index (M w / M n ) was determined by gel permeation chromatography. The specific test method was as follows: an HLC-8320 gel permeation chromatograph produced by Tosoh Corporation of Japan was used, the chromatographic column was TSKgelSuperMultiporeHZ-N, the standard column was TSKgelSuperMultiporeHZ, the solvent was chromatographically pure tetrahydrofuran (THF), and narrow distribution polystyrene was used as the standard sample. The polymer sample was prepared into a tetrahydrofuran solution with a concentration of 1 mg / mL, the injection volume was 10.00 μL, the flow rate was 0.35 mL / min, and the test temperature was 40.0°C.

[0038] In the present invention, the dynamic viscosity of the polymer is measured by the capillary method specified in GBT10247-2008, wherein the measurement is performed at a temperature of 45° C. using an Ubbelohde viscometer with a size of 5.

[0039] In the present invention, the content of metal elements in the polymer is determined by plasma method. The specific test method is as follows: using the Optima 8300 full-spectrum direct-reading ICP spectrometer of PerkinElmer (PE) of the United States, equipped with a medium-step grating, a solid-state detector, a dual-path dual solid-state detector in the ultraviolet and visible light regions, and using flat-panel plasma technology; the instrument operating parameters are as follows: high-frequency power 1300W, plasma gas flow rate 15L / min, atomizing gas flow rate 0.55L / min, auxiliary gas flow rate 0.2L / min, peristaltic pump speed 1.50mL / min, integration time 10s, plasma axial observation. The sample preparation method is as follows: accurately weigh 2.000g of sample into a porcelain crucible, place it in a high-temperature resistance furnace and gradually heat it to 500℃. After complete ashing, remove it, add 5mL of 10% by volume dilute nitric acid, slowly heat it on a hot plate until it is completely dissolved, evaporate the solution to dryness, add 1mL of concentrated nitric acid, transfer it to a 50mL volumetric flask, and make up to volume with water. At the same time, prepare a reagent blank solution.

[0040] In the present invention, the glass transition temperature of the liquid styrene butadiene polymer coating is determined by differential scanning calorimetry. The specific test method is: using a TA-2980DSC differential scanning calorimeter, determining according to the method specified in GB / T 29611-2013, with a heating rate of 20°C / min.

[0041] A first aspect of the present invention provides a liquid styrene butadiene polymer, characterized in that the liquid styrene butadiene polymer has the following characteristics:

[0042] (1) Based on the total weight of butadiene in the liquid styrene butadiene polymer, the 1,2-structure content of the liquid styrene butadiene polymer is 80-90% by weight;

[0043] (2) based on the total weight of the liquid styrene butadiene polymer, the styrene content in the liquid styrene butadiene polymer is 15-30% by weight, and the styrene block content is 0.1-0.5% by weight;

[0044] (3) the number average molecular weight of the liquid styrene-butadiene polymer is 1500-4500;

[0045] (4) the molecular weight distribution of the liquid styrene-butadiene polymer is 1.2-1.6;

[0046] (5) The dynamic viscosity of the liquid styrene-butadiene rubber at 45° C. is 100-500P.

[0047] In the present invention, the liquid styrene butadiene polymer has a high 1,2-structure content, thereby making the polymer coating containing the liquid styrene butadiene polymer have improved mechanical properties, a high glass transition temperature and excellent heat resistance.

[0048] In the present invention, when the number average molecular weight of the liquid styrene butadiene polymer meets the above range, it can ensure that the liquid styrene butadiene polymer has a suitable dynamic viscosity, and has good fluidity and processing performance when used to prepare a polymer coating, so that the prepared polymer coating is more uniform and the overall performance of the polymer coating is more excellent.

[0049] Furthermore, the number average molecular weight of the liquid styrene-butadiene polymer is 2000-4000, preferably 2500-3500.

[0050] In the present invention, when the molecular weight distribution of the liquid styrene butadiene polymer satisfies the above range, the liquid styrene butadiene polymer can have better processing and mechanical properties, thereby facilitating the preparation of a polymer coating with better performance. Specifically, if the molecular weight distribution of the liquid styrene butadiene polymer is too narrow, the processing properties of the liquid styrene butadiene polymer will deteriorate; if the molecular weight distribution of the liquid styrene butadiene polymer is too broad, the mechanical properties of the liquid styrene butadiene polymer will be reduced.

[0051] Furthermore, the molecular weight distribution of the liquid styrene-butadiene polymer is 1.25-1.55, preferably 1.3-1.5.

[0052] In the present invention, when the dynamic viscosity of the liquid styrene butadiene polymer at 45°C is too low, the liquid styrene butadiene polymer is easy to flow, and when the dynamic viscosity is too high, the liquid styrene butadiene polymer is not easy to coat. When the dynamic viscosity of the liquid styrene butadiene polymer at 45°C meets the above range, the liquid styrene butadiene polymer can have more excellent processing performance.

[0053] Furthermore, the dynamic viscosity of the liquid styrene-butadiene polymer at 45°C is 150-450P, preferably 200-400P.

[0054] In the present invention, a higher styrene content in the liquid styrene butadiene polymer increases its dynamic viscosity and glass transition temperature. However, an excessively high styrene content results in fewer crosslinkable double bonds in the liquid styrene butadiene polymer. The inventors have discovered that when the styrene content in the liquid styrene butadiene polymer is 15-30% by weight, the mechanical properties and heat resistance of the liquid styrene butadiene polymer are even better.

[0055] Furthermore, based on the total weight of the liquid styrene-butadiene polymer, the content of styrene in the liquid styrene-butadiene polymer is 17-25% by weight.

[0056] In the present invention, the higher the styrene block content in the liquid styrene butadiene polymer, the higher the glass transition temperature of the liquid styrene butadiene polymer, which is beneficial to improving the heat resistance of the final polymer coating. However, too high a styrene block content will lead to the formation of double bond vacuum in the molecular chain, which is not conducive to improving the mechanical properties of the final polymer coating. In order to make the polymer coating have excellent heat resistance and mechanical properties, the styrene block content is 0.1-0.5% by weight, preferably 0.2-0.4% by weight, based on the total weight of the liquid styrene butadiene polymer.

[0057] According to the present invention, the metal ion content of the liquid styrene-butadiene polymer is below 200 ppm.

[0058] In the present invention, the inventors have found that when the metal ion content of the liquid styrene butadiene polymer meets the above range, the dielectric properties of the liquid styrene butadiene polymer can be significantly improved, so that the polymer coating prepared therefrom has a low dielectric constant and low dielectric loss.

[0059] Furthermore, the metal ion content of the liquid styrene-butadiene polymer is below 100 ppm, preferably below 50 ppm, and more preferably below 20 ppm.

[0060] A second aspect of the present invention provides a method for preparing a liquid styrene-butadiene polymer, characterized in that the method comprises:

[0061] Under anionic polymerization conditions, 1,3-butadiene monomer, styrene monomer, 1,2-butadiene monomer, a structure regulator and an organic lithium initiator are contacted and reacted in a polymerization solvent to obtain the liquid styrene-butadiene polymer;

[0062] The temperature of the contact reaction is below 20°C;

[0063] The structure regulator comprises component A and component B; component A is selected from ether compounds and / or amine compounds; component B is an alkali metal alkoxide;

[0064] The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-12:1000;

[0065] The weight ratio of the 1,3-butadiene monomer to the styrene monomer is 2.3-5.7;

[0066] The molar ratio of the organic lithium initiator, the component A and the component B is 1:0.05-0.3:0.03-0.2, and the organic lithium initiator is calculated as lithium;

[0067] The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 1500-4500.

[0068] In the present invention, the above-mentioned method is used to prepare a liquid styrene butadiene polymer having not only a high vinyl content but also a moderate molecular weight distribution, and at the same time having a suitable molecular weight and dynamic viscosity, thereby making the liquid styrene butadiene polymer have good flow properties, film-forming properties and coating properties, and is particularly suitable for forming a polymer coating.

[0069] According to the present invention, the component A is selected from the compound represented by formula I and / or the compound represented by formula II;

[0070]

[0071] In formula I, R1 and R2 are the same or different and are each independently a hydrogen atom or a C1-C6 alkyl group,

[0072] R3 and R4 are the same or different and are each independently a C1-C6 alkyl group,

[0073] n is an integer from 1 to 5;

[0074]

[0075] In formula II, R5 and R6 are the same or different and are independently a hydrogen atom or a C1-C6 alkyl group,

[0076] R7 and R8 are the same or different and are independently C1-C6 alkylene. 10 、R 11 、R 12 、R 13 、R 14 、R 15 and R 16 The same or different, each independently a hydrogen atom or a C1-C6 alkyl group,

[0077] m is an integer from 1 to 5.

[0078] In the present invention, n is an integer of 1-5, and m is an integer of 1-5, for example, n can be 1, 2, 3, 4 or 5; m can be 2, 2, 3, 4 or 5.

[0079] In the present invention, in Formula I and Formula II, the C1-C6 alkyl group includes a C1-C6 straight-chain alkyl group and a C3-C6 branched-chain alkyl group, and specific examples thereof may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.

[0080] In a preferred embodiment of the present invention, in Formula I, R1 and R2 are both hydrogen atoms; R3 and R4 are the same, and are methyl, ethyl, n-propyl or n-butyl.

[0081] In a preferred embodiment of the present invention, in Formula II, R5 and R6 are both hydrogen atoms, R7 and R8 are C2-C4 alkylene groups, R9, R 10 、R 11 、R 12 、R 13 、R 14 、R 15 and R 16 All are hydrogen atoms.

[0082] According to the present invention, preferred examples of the component A may include, but are not limited to, at least one of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether and 1,2-dipiperidinylethane.

[0083] According to the present invention, the component B is a compound represented by formula III;

[0084] R 17 -OM Formula III

[0085] In formula III, R 17 C1-C 20 Alkyl, C6-C 30 Aryl or C4-C 20 Cycloalkyl;

[0086] M is an alkali metal atom.

[0087] In the present invention, in Formula III, C1-C 20 The alkyl groups include C1-C 20 Straight chain alkyl and C3-C 20 Specific examples of the branched alkyl group may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, undecyl and its isomers, dodecyl and its isomers, tridecyl and its isomers, tetradecyl and its isomers, pentadecyl and its isomers, hexadecyl and its isomers, heptadecyl and its isomers, octadecyl and its isomers, nonadecyl and its isomers, and eicosyl and its isomers.

[0088] In the present invention, in Formula III, C4-C 20 The cycloalkyl group includes cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl or 2-isopropyl-5-methylcyclohexyl.

[0089] Furthermore, in Formula III, R 17 C2-C 10Alkyl or C6-C 12 cycloalkyl, preferably C2-C6 alkyl; M is Li, Na or K, preferably Na.

[0090] According to the present invention, preferred examples of the component B may include, but are not limited to, at least one of sodium tert-butoxide, sodium tert-amyloxide, sodium menthol, sodium ethoxide, and sodium n-hexoxide.

[0091] According to the present invention, the molar ratio of the organic lithium initiator, the component A and the component B is 1:0.08-0.25:0.04-0.18, and the organic lithium initiator is calculated based on lithium.

[0092] Furthermore, the molar ratio of the organic lithium initiator, the component A and the component B is 1:0.1-0.2:0.05-0.15, and the organic lithium initiator is calculated as lithium.

[0093] According to the present invention, the molar ratio of the component A to the component B is 0.4-1.5:1, preferably 0.5-1:1.

[0094] According to the present invention, in order to further regulate the number average molecular weight and molecular weight distribution of the liquid styrene butadiene polymer so that the obtained liquid styrene butadiene polymer has a suitable number average molecular weight and molecular weight distribution, preferably, the weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-10:1000, preferably 3-9:1000. The larger the weight ratio of 1,2-butadiene to 1,3-butadiene, the wider the molecular weight distribution index.

[0095] According to the present invention, the weight ratio of the 1,3-butadiene monomer to the styrene monomer is 2.7-4.9:1, preferably 3-4.9:1.

[0096] According to the present invention, the amount of the organolithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 2000-4000, preferably 2500-3500. The method of determining the specific amount of the organolithium initiator according to the expected polymer molecular weight is well known to those skilled in the art and will not be described in detail herein.

[0097] According to the present invention, the organic lithium initiator is an organic monolithium compound.

[0098] Furthermore, the organic lithium initiator is a compound represented by formula IV;

[0099] R 18 Li Formula IV

[0100] In Formula IV, R 18 C1-C6 alkyl, C3-C 12 Cycloalkyl, C7-C14 Aralkyl or C6-C 12 of aromatic groups.

[0101] In the present invention, in formula IV, the C1-C6 alkyl group includes a C1-C6 straight-chain alkyl group and a C3-C6 branched-chain alkyl group, and specific examples thereof may include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.

[0102] In the present invention, in Formula IV, C3-C 12 Specific examples of the cycloalkyl group may include, but are not limited to, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-n-propylcyclohexyl group, and a 4-n-butylcyclohexyl group.

[0103] In the present invention, in Formula IV, C7-C 14 Specific examples of the aralkyl group may include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, phenylisopropyl, phenyl-n-pentyl, and phenyl-n-butyl.

[0104] In the present invention, in Formula IV, C6-C 12 Specific examples of the aryl group may include, but are not limited to, phenyl, naphthyl, 4-methylphenyl, and 4-ethylphenyl.

[0105] According to the present invention, specific examples of the organolithium initiator may include, but are not limited to, one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, 2-naphthyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, and 4-butylcyclohexyllithium. Preferably, the organolithium initiator is n-butyllithium and / or sec-butyllithium, and more preferably, the organolithium initiator is n-butyllithium.

[0106] In the present invention, the polymerization solvent can be any organic substance that can serve as a reaction medium and allow the polymerization reaction to proceed under solution polymerization conditions, for example, a hydrocarbon solvent. The polymerization solvent can be one or more selected from cyclohexane, n-hexane, n-pentane, n-heptane, benzene, and raffinate oil. The raffinate oil is the distillate remaining after the aromatics are extracted from the catalytic reforming product rich in aromatics during the petroleum refining process. The polymerization solvent can be used alone or in combination.

[0107] According to the present invention, the total content of 1,3-butadiene and styrene monomers (i.e., total monomer content) can be 1-20% by weight, preferably 6-14% by weight, based on the total amount of the polymerization solvent and the 1,3-butadiene and styrene monomers. In the present invention, the total monomer content refers to the weight percentage of the 1,3-butadiene and styrene monomers determined based on the total amount of the polymerization solvent, 1,3-butadiene, and styrene before the polymerization reaction.

[0108] According to the present invention, the temperature of the contact reaction is -10°C to 20°C, for example, 1,3-butadiene is contacted with the structure regulator and the organolithium initiator at a temperature of -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C or 20°C. Preferably, 1,3-butadiene, styrene, the structure regulator and the organolithium initiator are contacted at a temperature not higher than 10°C, such as at a temperature of -5°C to 10°C.

[0109] In the present invention, the anionic polymerization reaction can be carried out at a pressure of 0.005-1.5 MPa, more preferably at a pressure of 0.1-1 MPa. In the present invention, the pressure refers to the gauge pressure. According to the preparation method of the present invention, the time of the anionic polymerization reaction can be selected according to the temperature of the polymerization reaction, generally 30-240 min, preferably 40-120 min.

[0110] In the present invention, the anionic polymerization reaction is carried out in an atmosphere formed by an inert gas. The inert gas refers to a gas that does not chemically interact with the reactants, reaction products, and solvent under polymerization conditions, such as nitrogen and / or a Group 0 element gas (such as argon).

[0111] According to the present invention, the preparation method may further include: removing at least a portion of metal ions from the polymerization reaction mixture obtained by the contact reaction to obtain the liquid styrene-butadiene polymer. Specifically, the polymerization reaction mixture may be washed to remove at least a portion of the metal ions.

[0112] In a preferred embodiment of the present invention, the method for removing at least part of the metal ions in the polymerization reaction mixture comprises: mixing and separating the polymerization reaction mixture obtained by the contact reaction with a washing liquid to separate the oil phase from the mixture to obtain the liquid styrene-butadiene polymer. The washing liquid is water or an aqueous solution containing an acid. In a preferred embodiment, the acid is preferably an inorganic acid, more preferably one or more of sulfuric acid, nitric acid, hydrochloric acid and carbonic acid. When the acid is carbonic acid, carbonic acid can be formed by passing carbon dioxide gas into the mixture of the polymerization reaction mixture and water and / or adding dry ice to the polymerization reaction mixture.

[0113] In a preferred embodiment of the present invention, the washing liquid includes a first washing liquid and a second washing liquid, the first washing liquid is an aqueous solution containing at least one acid selected from sulfuric acid, hydrochloric acid and nitric acid; the second aqueous solution is an aqueous solution containing carbonic acid.

[0114] Furthermore, in the present invention, the preparation method comprises: S1, mixing and separating the polymerization reaction mixture obtained by the contact reaction with a first washing liquid to obtain a first oil phase, and removing at least part of the polymerization solvent in the first oil phase to obtain a crude liquid styrene-butadiene polymer product;

[0115] S2. Mixing and separating the crude liquid styrene butadiene polymer product with a second washing liquid to obtain a second oil phase, and removing at least part of the volatile components in the second oil phase to obtain the liquid styrene butadiene polymer.

[0116] In a preferred embodiment of the present invention, the weight ratio of the first washing liquid to 1,3-butadiene and styrene monomer is preferably 0.5-5:1, more preferably 2-4:1. + The molar ratio of the acid in the first washing solution to the organic lithium initiator, calculated as lithium, is preferably 0.1-1.5:1, more preferably 0.2-1.2:1, and further preferably 0.5-1.1:1.

[0117] In a preferred embodiment of the present invention, the weight ratio of the second washing liquid to 1,3-butadiene and styrene monomer is 1-2:1. + The molar ratio of the acid in the second washing solution to the organic lithium initiator, calculated as lithium, is preferably 0.1-0.6:1, more preferably 0.2-0.5:1, and further preferably 0.3-0.4:1.

[0118] The third aspect of the present invention provides a liquid styrene-butadiene polymer prepared by the above preparation method.

[0119] In the present invention, the liquid styrene butadiene polymer prepared by the above-mentioned preparation method has a high vinyl content and a moderate molecular weight distribution, and at the same time has an appropriate molecular weight and dynamic viscosity, thereby making the liquid styrene butadiene polymer have good flowability, film-forming properties and coating properties. In particular, the coating formed by the coating containing the liquid styrene butadiene polymer of the present invention has excellent mechanical properties and heat resistance.

[0120] A fourth aspect of the present invention provides a composition, characterized in that the composition contains a liquid styrene butadiene polymer and at least one additive, wherein the liquid styrene butadiene polymer is the above-mentioned liquid styrene butadiene polymer.

[0121] In the present invention, the additive can be a substance that can give the composition new properties and / or improve the existing properties of the composition. As a preferred example, the additive contains an antioxidant. The antioxidant can be a conventional selection, for example, the antioxidant can be a phenolic and / or amine antioxidant. Specifically, the antioxidant can be one or more of 4,6-dioctylthiomethyl o-cresol, tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester (i.e., Antioxidant 264), tris(2,4-di-tert-butylphenyl) phosphite (i.e., Antioxidant 168), 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester (i.e., Antioxidant 1076), 2,6-di-tert-butyl-p-cresol, tert-butylcatechol and 2,2'-methylene-bis(4-methyl-6-tert-butylphenol). Relative to 100 parts by weight of the liquid styrene-butadiene polymer, the content of the antioxidant may be 0.005-2 parts by weight, preferably 0.01-1 part by weight.

[0122] A fifth aspect of the present invention provides a polymer coating, characterized in that the polymer coating contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0123] In the present invention, the polymer coating containing the above-mentioned styrene-butadiene polymer or composition has high adhesion to the substrate and heat resistance.

[0124] A sixth aspect of the present invention provides an adhesive, characterized in that the adhesive contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0125] A seventh aspect of the present invention provides a cross-linking agent, characterized in that the cross-linking agent contains the above-mentioned liquid styrene-butadiene polymer or the above-mentioned composition.

[0126] An eighth aspect of the present invention provides the use of the liquid styrene-butadiene polymer or the composition as a cross-linking agent, adhesive or electrical insulating material.

[0127] Unless otherwise specified, normal temperature and room temperature both mean 25±3°C.

[0128] The present invention will be described in detail below through examples.

[0129] In the following examples and comparative examples, the 1,2-structural unit content, styrene block content and styrene content of the liquid polybutadiene styrene polymer were measured using a Bruker AVANCE400 superconducting nuclear magnetic resonance instrument. 1 The resonance frequency of the H nucleus is 300.13 MHz, the spectral width is 2747.253 Hz, the pulse width is 5.0 μs, the data point is 16 K, the sample tube diameter is 5 mm, the solvent is deuterated chloroform (CDCl3), the sample concentration is 15 mg / mL, the test temperature is room temperature, the number of scans is 16 times, and the calibration is based on the tetramethylsilane chemical shift of 0 ppm.

[0130] In the following examples and comparative examples, the molecular weight and molecular weight distribution index of the liquid styrene-butadiene polymer were determined by gel permeation chromatography analysis. The gel permeation chromatography analysis adopted an HLC-8320 gel permeation chromatograph produced by Tosoh Corporation of Japan, the chromatographic column was TSKgelSuperMultiporeHZ-N, the standard column was TSKgelSuperMultiporeHZ, the solvent was chromatographically pure tetrahydrofuran (THF), and narrow distribution polystyrene was used as the standard sample. The polymer sample was prepared into a tetrahydrofuran solution with a mass concentration of 1 mg / mL, the injection volume was 10.00 μL, the flow velocity was 0.35 mL / min, and the test temperature was 40.0°C.

[0131] In the following examples and comparative examples, the content of metal elements in liquid styrene-butadiene polymer was determined by a plasma method. The specific test method was as follows: an Optima 8300 full-spectrum direct-reading ICP spectrometer produced by PerkinElmer (PE) of the United States was used, equipped with a medium-step grating, a solid-state detector, a dual-path dual-solid-state detector in the ultraviolet light region and the visible light region, and a flat-panel plasma technology; the instrument operating parameters were as follows: high-frequency power 1300 W, plasma gas flow rate 15 L / min, atomizing gas flow rate 0.55 L / min, auxiliary gas flow rate 0.2 L / min, peristaltic pump speed 1.50 mL / min, integration time 10 s, and plasma axial observation. The sample preparation method is as follows: accurately weigh 2.000 g of sample into a porcelain crucible, place it in a high-temperature resistance furnace and gradually heat it to 500°C. After complete ashing, take it out and add 5 mL of 10% (V%) dilute nitric acid. Slowly heat on a hot plate until it is completely dissolved. Evaporate the solution to dryness, add 1 mL of concentrated nitric acid (concentration of 68 volume%), transfer it to a 50 mL volumetric flask, and make up to volume with water. At the same time, prepare a reagent blank solution.

[0132] In the following examples and comparative examples, the dynamic viscosity of the liquid styrene-butadiene polymer at 45°C was measured by the capillary method specified in GBT10247-2008, wherein the viscosity was measured at 45°C using an Ubbelohde viscometer with a size of 4B.

[0133] The following chemical reagents are involved in the following examples and comparative examples:

[0134] Antioxidant 264, antioxidant 168, and antioxidant 1076 were purchased from Sinopharm Reagent Company;

[0135] Cyclohexane: purchased from Sinopharm Reagent Company, purity >99.9%, soaked in molecular weight sieve for 15 days, water content less than 5ppm (weight content);

[0136] 1,3-Butadiene: polymer grade, purchased from Yanshan Petrochemical;

[0137] Styrene: polymer grade, purchased from Yanshan Petrochemical;

[0138] 1,2-Butadiene, purity >97%, provided by Beijing Qingkai Huafeng Reagent Co., Ltd.

[0139] n-Butyl lithium: purchased from J&K Reagent Co., Ltd. as a 1.6 mol / L hexane solution;

[0140] Diethylene glycol dimethyl ether (2G, molecular weight 134): purchased from J&K Reagent Co., analytical grade;

[0141] Diethylene glycol diethyl ether: purchased from J&K Reagent Co., analytical grade;

[0142] Ditetrahydrofurfurylpropane (DTHFP): purchased from J&K Reagent Co., Ltd., purity >98%;

[0143] 1,2-Dipiperidinylethane (DPE, molecular weight 196): purchased from J&K Reagent Co., analytical grade;

[0144] Sodium tert-amyloxide (STA, molecular weight 110): purchased from J&K Reagent Co., Ltd., 1.4 mol / L tetrahydrofuran solution;

[0145] Sodium ethoxide (SEO, molecular weight 68): purchased from J&K Reagent Co., Ltd., purity 96%, prepared into a 0.2 mol / L tetrahydrofuran solution;

[0146] Sulfuric acid: purchased from J&K Reagent Co., Ltd., concentration is 98 wt%, prepared with water to make a 20 wt% solution;

[0147] Nitric acid: purchased from Sinopharm Reagent Company with a concentration of 68 wt %, prepared into a 20 wt % solution with water.

[0148] Example 1

[0149] This embodiment is used to illustrate the liquid styrene-butadiene polymer and its preparation method of the present invention.

[0150] (1) Under nitrogen protection, cyclohexane, structure regulator A, structure regulator B, styrene, 1,3-butadiene, and 1,2-butadiene (the types and amounts are shown in Table 1, and the amounts listed in the table are all measured based on pure compounds) are added to a 5 L reactor, the reactor temperature is controlled to be below 10°C, and a designed amount of n-butyl lithium (the amount is shown in Table 1, and the amounts listed in the table are all measured based on pure compounds) is added to the 5 L reactor; and an anionic polymerization reaction is carried out at the temperature and reaction pressure listed in Table 1 to obtain a reaction mixture containing a liquid butadiene-styrene polymer.

[0151] (2) Add water and acid (the specific amounts and types of acids are listed in Table 2, and the amounts listed in the table are all measured based on pure compounds) to the polymerization reaction mixture obtained in step (1), stir for 15 minutes, and then stand for stratification to separate the aqueous phase. The obtained oil phase is subjected to reduced pressure distillation to remove the crude liquid styrene butadiene polymer.

[0152] (3) Water is added to the crude liquid styrene butadiene polymer obtained in step (2), and carbon dioxide gas is introduced with stirring (the specific amounts of water and carbon dioxide are listed in Table 2). The mixture is then allowed to stand for stratification to separate the aqueous phase. The resulting oil phase is subjected to reduced pressure distillation, and an antioxidant is added to the distillation residue (the specific amount and type are listed in Table 2) to obtain a composition BS1 containing the liquid styrene butadiene polymer according to the present invention. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0153] Example 2-12

[0154] Examples 2-12 are used to illustrate the liquid styrene-butadiene polymer and its preparation method of the present invention.

[0155] Examples 2-12 use the same method as Example 1 to prepare liquid styrene butadiene polymers, except that the liquid styrene butadiene polymer compositions BS2-BS12 according to the present invention are prepared under the conditions listed in Tables 1 and 2, wherein the structural property parameters of the prepared liquid styrene butadiene polymers are listed in Table 3.

[0156] Comparative Example 1

[0157] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that the amount of structure regulator A diethylene glycol dimethyl ether used in step (1) was 0.5 g, and a composition DBS1 containing liquid styrene butadiene polymer was obtained. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0158] Comparative Example 2

[0159] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that the structure regulator B, sodium tert-pentoxide, was not used in step (1), but only diethylene glycol dimethyl ether was used as the structure regulator A, to obtain a composition DBS2 containing a liquid styrene butadiene polymer. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0160] Comparative Example 3

[0161] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that in step (1), the polymerization reaction temperature was 50°C, and a composition DBS3 containing liquid styrene butadiene polymer was obtained. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0162] Comparative Example 4

[0163] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that the structure regulator A in step (1) was ditetrahydrofurfuryl propane, to obtain a composition DBS4 containing a liquid styrene butadiene polymer. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0164] Comparative Example 5

[0165] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that 4 g of 1,2-butadiene was added in step (1) to obtain a composition DBS5 containing a liquid styrene butadiene polymer. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0166] Comparative Example 6

[0167] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that the amount of styrene added in step (1) was 90 g and the amount of 1,3-butadiene added was 160 g, to obtain a composition DBS6 containing a styrene butadiene polymer. The structural property parameters of the prepared styrene butadiene polymer are listed in Table 3.

[0168] Comparative Example 7

[0169] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that in step (1), the amount of n-butyl lithium used was 50 mmol, and a composition DBS7 containing liquid styrene butadiene polymer was obtained. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0170] Comparative Example 8

[0171] Liquid styrene butadiene polymer was prepared by the same method as in Example 1, except that in step (1), the amount of n-butyl lithium used was 200 mmol, and a composition DBS8 containing liquid styrene butadiene polymer was obtained. The structural property parameters of the prepared liquid styrene butadiene polymer are listed in Table 3.

[0172] Table 1

[0173]

[0174]

[0175] Table 1 (Continued)

[0176] Example 7 8 9 10 11 12 Type of polymerization solvent Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Polymerization solvent dosage / g 2300 2300 2300 2300 2300 2300 Styrene dosage / g 40 70 50 50 50 50 1,3-Butadiene dosage / g 210 180 200 200 200 200 1,2-Butadiene dosage / g 1.2 1.5 2 1.5 0.5 2 n-Butyl lithium dosage / mmol 120 85 160 60 85 85 Structural Modifier A 2G 2G 2G DPE Diethylene glycol diethyl ether 2G Structure regulator A / g 2 2 3 2 2 2 Structural Modifier B STA STA STA SEO SEO STA Structure modifier B / mmol 12 8 16 6 8 8 Polymerization reaction temperature 10℃ 10℃ 0℃ 10℃ 10℃ 10℃ Polymerization reaction pressure 0.3MPa 0.3MPa 0.3MPa 0.3MPa 0.3MPa 0.3MPa Polymerization reaction time 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes

[0177] Table 2

[0178]

[0179] Table 3

[0180]

[0181] 1 :Based on the total amount of styrene-butadiene polymer, the content of 1,2-structural units

[0182] 2 :Based on the total amount of styrene butadiene polymer, the content of styrene structural units

[0183] 3 :Based on the total amount of styrene-butadiene polymer, the content of block styrene structural units

[0184] Test Case

[0185] The compositions prepared in Examples 1 to 12 were uniformly coated on a copper foil surface to a coating thickness of 0.6 mm. The coating was cross-linked and cured at 120° C. for 2 hours. The peel strength was measured using the method specified in IPC-TM-650 2.4.08C. The dielectric constant and dielectric loss were measured using a stripline resonant cavity method in accordance with GB / T 12636-90. The glass transition temperature was measured using a TA-2980DSC differential scanning calorimeter. The experimental results are listed in Table 4.

[0186] Test comparison

[0187] The peel strength, glass transition temperature, dielectric constant and dielectric loss of the compositions prepared in Comparative Examples 1-8 were measured using the same method as in the test example. The experimental results are listed in Table 4.

[0188] Table 4

[0189]

[0190] As can be seen from Tables 3 and 4, the liquid styrene butadiene polymer of the present invention not only has a high 1,2-structural unit content and a suitable molecular weight distribution, but also has a moderate molecular weight and dynamic viscosity at 45°C, good flow properties, good coating properties and film-forming properties, and the polymer coating formed after cross-linking and curing has a strong adhesion to the substrate, a high glass transition temperature, and good heat resistance. At the same time, the polymer coating prepared from the liquid styrene butadiene polymer of the present invention has a low dielectric constant and low dielectric loss. Among them, the dynamic viscosity of the liquid styrene butadiene polymer prepared in Comparative Example 7 is too large, and the dynamic viscosity of the liquid styrene butadiene polymer prepared in Comparative Example 8 is small. The coating properties and film-forming properties of the two are poor, and it is difficult to form a polymer coating with uniform thickness and uniform performance.

[0191] In addition, the liquid styrene butadiene polymer according to the present invention has a low metal ion content. The liquid styrene butadiene polymer according to the present invention is suitable as a crosslinking agent, adhesive or electrical insulation material.

[0192] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A liquid styrene-butadiene polymer, characterized in that The liquid styrene butadiene polymer has the following characteristics: (1) Based on the total weight of butadiene in the liquid styrene butadiene polymer, the 1,2-structure content of the liquid styrene butadiene polymer is 80-90% by weight; (2) Based on the total weight of the liquid styrene butadiene polymer, the styrene content in the liquid styrene butadiene polymer is 15-30% by weight, and the styrene block content is 0.1-0.5% by weight; (3) The number average molecular weight of the liquid styrene-butadiene polymer is 1500-4500; (4) The molecular weight distribution of the liquid styrene-butadiene polymer is 1.2-1.6; (5) The dynamic viscosity of the liquid styrene-butadiene polymer at 45°C is 100-500P.

2. The liquid styrene-butadiene polymer according to claim 1, wherein Based on the total weight of the liquid styrene butadiene polymer, the styrene content in the liquid styrene butadiene polymer is 17-25% by weight.

3. The liquid styrene-butadiene polymer according to claim 1, wherein Based on the total weight of the liquid styrene butadiene polymer, the styrene block content in the liquid styrene butadiene polymer is 0.2-0.4 weight %.

4. The liquid styrene-butadiene polymer according to claim 1, wherein The number average molecular weight of the liquid styrene-butadiene polymer is 2000-4000.

5. The liquid styrene-butadiene polymer according to claim 1, wherein The number average molecular weight of the liquid styrene-butadiene polymer is 2500-3500.

6. The liquid styrene-butadiene polymer according to claim 1, wherein The molecular weight distribution of the liquid styrene-butadiene polymer is 1.25-1.

55.

7. The liquid styrene-butadiene polymer according to claim 1, wherein The molecular weight distribution of the liquid styrene-butadiene polymer is 1.3-1.

5.

8. The liquid styrene-butadiene polymer according to claim 1, wherein The dynamic viscosity of the liquid styrene-butadiene polymer at 45° C. is 150-450P.

9. The liquid styrene-butadiene polymer according to claim 1, wherein The dynamic viscosity of the liquid styrene-butadiene polymer at 45° C. is 200-400P.

10. The liquid styrene-butadiene polymer according to claim 1, wherein The metal ion content of the liquid styrene-butadiene polymer is below 200 ppm.

11. The liquid styrene-butadiene polymer according to claim 1, wherein The metal ion content of the liquid styrene-butadiene polymer is below 100 ppm.

12. The liquid styrene-butadiene polymer according to claim 1, wherein The metal ion content of the liquid styrene-butadiene polymer is below 50 ppm.

13. The liquid styrene-butadiene polymer according to claim 1, wherein The metal ion content of the liquid styrene-butadiene polymer is below 20 ppm.

14. A method for preparing a liquid styrene-butadiene polymer, characterized in that: The method comprises: Under anionic polymerization conditions, 1,3-butadiene monomer, styrene monomer, 1,2-butadiene monomer, a structure regulator and an organic lithium initiator are contacted and reacted in a polymerization solvent to obtain the liquid styrene-butadiene polymer; The temperature of the contact reaction is below 20°C; The structure regulator comprises component A and component B; component A is selected from ether compounds and / or amine compounds; component B is an alkali metal alkoxide; The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-12:1000; The weight ratio of the 1,3-butadiene monomer to the styrene monomer is 2.3-5.7:1; The molar ratio of the organic lithium initiator, the component A and the component B is 1:0.05-0.3:0.03-0.2, and the organic lithium initiator is calculated as lithium; The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 1500-4500.

15. The preparation method according to claim 14, wherein The component A is selected from the compound represented by formula I and / or the compound represented by formula II; Formula I In formula I, R1 and R2 are the same or different and are each independently a hydrogen atom or a C1-C6 alkyl group, R3 and R4 are the same or different and are each independently a C1-C6 alkyl group, n is an integer from 1 to 5; Formula II In formula II, R5 and R6 are the same or different and are independently a hydrogen atom or a C1-C6 alkyl group, R7 and R8 are the same or different and are independently C1-C6 alkylene. 10 、R 11 、R 12 、R 13 、R 14 、R 15 and R 16 The same or different, each independently a hydrogen atom or a C1-C6 alkyl group, m is an integer from 1 to 5.

16. The preparation method according to claim 14, wherein The component A is selected from at least one of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether and 1,2-dipiperidinylethane.

17. The preparation method according to claim 14, wherein The component B is a compound represented by formula III; Formula III In formula III, R 17 C1-C 20 Alkyl, C6-C 30 Aryl or C4-C 20 Cycloalkyl; M is an alkali metal atom.

18. The preparation method according to claim 14, wherein The component B is at least one selected from sodium tert-butoxide, sodium tert-amyloxide, sodium menthol, sodium ethoxide and sodium n-hexoxide.

19. The preparation method according to claim 14, wherein The molar ratio of the organic lithium initiator, the component A and the component B is 1:0.08-0.25:0.04-0.18, and the organic lithium initiator is calculated based on lithium.

20. The preparation method according to claim 14, wherein The molar ratio of the component A to the component B is 0.4-1.5:

1.

21. The preparation method according to claim 14, wherein The molar ratio of the component A to the component B is 0.5-1:

1.

22. The preparation method according to claim 14, wherein The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-10:1000.

23. The preparation method according to claim 14, wherein The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 3-9:1000.

24. The preparation method according to claim 14, wherein The weight ratio of the 1,3-butadiene monomer to the styrene monomer is 2.7-4.9:

1.

25. The preparation method according to claim 14, wherein The weight ratio of the 1,3-butadiene monomer to the styrene monomer is 3-4.9:

1.

26. The preparation method according to claim 14, wherein The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 2000-4000.

27. The preparation method according to claim 14, wherein The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid styrene-butadiene polymer is 2500-3500.

28. The preparation method according to claim 14, wherein The organic lithium initiator is a compound shown in formula IV; R 18 Formula IV of Li In Formula IV, R 18 C1-C6 alkyl, C3-C 12 Cycloalkyl, C7-C 14 Aralkyl or C6-C 12 of aromatic groups.

29. The preparation method according to claim 14, wherein Based on the total amount of the polymerization solvent, the 1,3-butadiene monomer and the styrene monomer, the total content of the 1,3-butadiene monomer and the styrene monomer is 1-20 wt %.

30. The preparation method according to claim 14, wherein Based on the total amount of the polymerization solvent, the 1,3-butadiene monomer and the styrene monomer, the total content of the 1,3-butadiene monomer and the styrene monomer is 6-14 wt %.

31. The preparation method according to claim 14, wherein The temperature of the contact reaction is -5°C to 20°C.

32. The preparation method according to claim 14, wherein The preparation method further comprises: removing at least part of the metal ions in the polymerization reaction mixture obtained by the contact reaction to obtain the liquid styrene-butadiene polymer.

33. The preparation method according to claim 14, wherein The preparation method comprises: mixing a polymerization reaction mixture obtained by a contact reaction with a washing liquid, and separating the mixture to obtain the liquid styrene-butadiene polymer.

34. The preparation method according to claim 33, wherein The washing liquid is water or an aqueous solution containing acid.

35. The preparation method according to claim 33, wherein The washing liquid includes a first washing liquid and a second washing liquid.

36. The preparation method according to claim 35, wherein The first washing liquid is an aqueous solution containing at least one acid selected from sulfuric acid, hydrochloric acid and nitric acid; the second washing liquid is an aqueous solution containing carbonic acid.

37. The preparation method according to claim 14, wherein The preparation method further comprises: S1, mixing and separating the polymerization reaction mixture obtained by the contact reaction with a first washing liquid to obtain a first oil phase, and removing at least a portion of the polymerization solvent in the first oil phase to obtain a crude liquid styrene-butadiene polymer product; S2. Mixing and separating the crude liquid styrene butadiene polymer product and a second washing liquid to obtain a second oil phase, and removing at least part of the volatile components in the second oil phase to obtain the liquid styrene butadiene polymer.

38. The preparation method according to claim 37, wherein The weight ratio of the first washing liquid to the total weight of the 1,3-butadiene monomer and the styrene monomer is 0.5-5:

1.

39. The preparation method according to claim 37, wherein H + The molar ratio of the acid in the first washing solution to the organic lithium initiator, calculated as lithium, is 0.1-1.5:

1.

40. The preparation method according to claim 37, wherein The weight ratio of the second washing liquid to the total weight of the 1,3-butadiene monomer and the styrene monomer is 1-2:

1.

41. The preparation method according to claim 37, wherein H + The molar ratio of the acid in the second washing solution to the organic lithium initiator, calculated as lithium, is 0.1-0.6:

1.

42. A liquid styrene-butadiene polymer obtained by the preparation method described in any one of claims 14 to 41.

43. A composition, characterized in that The composition contains a liquid styrene butadiene polymer and at least one additive, wherein the liquid styrene butadiene polymer is the liquid styrene butadiene polymer according to any one of claims 1 to 13 and 42.

44. The additive according to claim 43, wherein The additives include antioxidants.

45. A polymer coating, characterized in that The polymer coating comprises the liquid styrene-butadiene polymer described in any one of claims 1-13 and 42, or the composition described in claim 43.

46. ​​An adhesive, characterized in that The adhesive contains the liquid styrene-butadiene polymer described in any one of claims 1-13 and 42, or the composition described in claim 43.

47. A cross-linking agent, characterized in that The cross-linking agent contains the liquid styrene-butadiene polymer described in any one of claims 1-13 and 42, or the composition described in claim 43.

48. Use of the liquid styrene-butadiene polymer according to any one of claims 1 to 13 and 42, or the composition according to claim 43 as a cross-linking agent, adhesive or electrical insulating material.

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