Liquid polybutadiene, 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 polybutadiene and a preparation method and application thereof, a composition and application thereof, a polymer coating, an adhesive, and a cross-linking agent. The liquid polybutadiene has an Mn of 1500-4500; an Mw / Mn of 1.21-1.59; based on the total weight of the liquid polybutadiene, the content of 1,2-structural units is 85-95wt%, and the content of 1,4-structural units is 5-15wt%; the molar ratio of cis-1,4-structural units to trans-1,4-structural units is 1-2:1; and the dynamic viscosity of the liquid polybutadiene at 45°C is 100-500P. The liquid polybutadiene rubber has a high vinyl content, suitable Mw / Mn, Mn, and dynamic viscosity. The liquid polybutadiene has good flow properties, good film-forming and coating properties, and when used to form a polymer coating, it can significantly improve the adhesion of the polymer coating to a substrate.

Description

Technical Field

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

[0002] Liquid polybutadiene is a viscous, flowable polymer with a number-average molecular weight of 500-10,000. It is an oily liquid at room temperature and has a wide range of uses in coatings, inks, surfactants, and polymer modifiers.

[0003] According to the microstructure classification, liquid polybutadiene can be divided into 1,4-addition (cis and trans isomers) and 1,2-addition products. Among the 1,2-addition products, according to the vinyl content, they can be divided into medium-vinyl liquid polybutadiene and high-vinyl liquid polybutadiene.

[0004] High-vinyl liquid polybutadiene refers to liquid polybutadiene with a 1,2-structure content of more than 65% by weight. High-vinyl liquid polybutadiene is generally prepared using iron-based, cobalt-based, and molybdenum-based catalysts. However, the above catalyst systems have the following disadvantages: (1) it is difficult to prepare low-molecular-weight liquid polybutadiene; (2) the molecular weight distribution is wide and the peel strength is low; and (3) it contains variable-valence metals, which affects the color of the product.

[0005] Therefore, there is an urgent need to develop liquid polybutadiene with high vinyl content and moderate molecular weight distribution. Summary of the Invention

[0006] The present invention aims to overcome the problem of wide molecular weight distribution of high-vinyl liquid polybutadiene in the prior art by providing a liquid polybutadiene, a preparation method and application thereof, a composition and application thereof, a polymer coating, an adhesive, and a crosslinking agent. The liquid polybutadiene rubber has a high vinyl content and a moderate molecular weight distribution, as well as an appropriate molecular weight and dynamic viscosity. This liquid polybutadiene exhibits good flow properties, film-forming properties, and coating performance. When used to form a polymer coating, it can significantly improve the adhesion of the polymer coating to a substrate.

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

[0008] (1) The number average molecular weight of the liquid polybutadiene is 1500-4500;

[0009] (2) the molecular weight distribution index of the liquid polybutadiene is 1.21-1.59;

[0010] (3) Based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight;

[0011] (4) The molar ratio of cis-1,4-structural units to trans-1,4-structural units in the liquid polybutadiene is 1-2:1;

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

[0013] A second aspect of the present invention provides a method for preparing liquid polybutadiene, characterized in that the method comprises the following steps:

[0014] Under anionic polymerization conditions, 1,3-butadiene 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 polybutadiene;

[0015] Wherein, the temperature of the contact reaction is -10°C to 20°C;

[0016] The structure regulator contains component A and component B, wherein component A is selected from ether compounds and / or amine compounds; and component B is selected from alkali metal alcoholates.

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

[0018] 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;

[0019] The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid polybutadiene is 1500-4500.

[0020] The third aspect of the present invention provides a liquid polybutadiene prepared by the above preparation method.

[0021] A fourth aspect of the present invention provides a composition, characterized in that the composition contains liquid polybutadiene and at least one additive, and the liquid polybutadiene is the above-mentioned liquid polybutadiene.

[0022] A fifth aspect of the present invention provides a polymer coating, characterized in that the polymer coating contains the above-mentioned liquid polybutadiene or the above-mentioned composition.

[0023] A sixth aspect of the present invention provides an adhesive, characterized in that the adhesive contains the above-mentioned liquid polybutadiene or the above-mentioned composition.

[0024] A seventh aspect of the present invention provides a cross-linking agent, characterized in that the cross-linking agent contains the above-mentioned liquid polybutadiene or the above-mentioned composition.

[0025] An eighth aspect of the present invention provides use of the liquid polybutadiene or the composition as a cross-linking agent, adhesive or electrical insulating material.

[0026] Through the above technical solution, the liquid polybutadiene and its preparation method and application, composition and application, polymer coating, adhesive and crosslinking agent provided by the present invention achieve the following beneficial effects:

[0027] The liquid polybutadiene provided by the present invention not only has a high vinyl content but also has a moderate molecular weight distribution, and also has a suitable molecular weight and dynamic viscosity. As a result, the liquid polybutadiene has good flowability, film-forming properties, and coating properties, making it particularly suitable for forming polymer coatings.

[0028] Furthermore, the polymer coating formed by the liquid polybutadiene provided by the present invention has good adhesion to the substrate.

[0029] Furthermore, the liquid polybutadiene provided by the present invention has good application prospects in the fields of cross-linking agents, adhesives, electrical insulation materials and communication technology. DETAILED DESCRIPTION

[0030] 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.

[0031] A first aspect of the present invention provides a liquid polybutadiene, characterized in that the liquid polybutadiene has the following characteristics:

[0032] (1) The number average molecular weight of the liquid polybutadiene is 1500-4500;

[0033] (2) the molecular weight distribution index of the liquid polybutadiene is 1.21-1.59;

[0034] (3) Based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight;

[0035] (4) The molar ratio of cis-1,4-structural units to trans-1,4-structural units in the liquid polybutadiene is 1-2:1;

[0036] (5) The dynamic viscosity of the liquid polybutadiene at 45°C is 100-500P.

[0037] In the present invention, the term "liquid polybutadiene" refers to polybutadiene having fluidity at a temperature of 25°C.

[0038] In the present invention, the term "1,2-structural unit" refers to a structural unit formed by 1,2-polymerization of butadiene. The content of 1,2-structural units may also be referred to as vinyl content. In the present invention, the term "1,4-structural unit" refers to a structural unit formed by 1,4-polymerization of butadiene.

[0039] In the present invention, the sum of the content of the 1,2-structural unit and the content of the 1,4-structural unit in the liquid polybutadiene is 100% by weight.

[0040] In the present invention, the term "cis 1,4-structural unit" refers to a structural unit formed by 1,4-polymerization of butadiene and having a cis configuration, that is, a structural unit shown in the following formula:

[0041]

[0042] In the present invention, the term "trans 1,4-structural unit" refers to a structural unit formed by 1,4-polymerization of butadiene and having a trans configuration, that is, a structural unit shown in the following formula:

[0043]

[0044] In the present invention, the liquid polybutadiene not only has a high vinyl content but also has a moderate molecular weight distribution, and also has a suitable molecular weight and dynamic viscosity. As a result, the liquid polybutadiene has good flowability, film-forming properties, and coating properties, and is particularly suitable for forming polymer coatings.

[0045] In the present invention, the molecular weight and molecular weight distribution index of the liquid polybutadiene are determined by gel permeation chromatography analysis. The gel permeation chromatography analysis adopts an HLC-8320 gel permeation chromatograph produced by Tosoh Corporation of Japan, a chromatographic column is TSKgel Super Multipore HZ-N, a standard column is TSKgel Super Multipore HZ, a solvent is chromatographically pure tetrahydrofuran (THF), and narrow distribution polystyrene is used as a standard sample. The polymer sample is prepared into a tetrahydrofuran solution with a mass concentration of 1 mg / mL, the injection volume is 10.00 μL, the flow rate is 0.35 mL / min, and the test temperature is 40.0°C.

[0046] In the present invention, the contents of 1,2-structural unit, 1,4-structural unit, cis-1,4-structural unit, and trans-1,4-structural unit are all determined by nuclear magnetic resonance spectroscopy. The specific testing method is: using a Bruker AVANCE400 superconducting nuclear magnetic resonance wave instrument for testing. 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.

[0047] In the present invention, the dynamic viscosity 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 4B.

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

[0049] Furthermore, the number average molecular weight of the liquid polybutadiene is 1800-4000, preferably 2000-3800.

[0050] In the present invention, when the molecular weight distribution of the liquid polybutadiene satisfies the above range, the liquid polybutadiene 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 polybutadiene is too narrow, the processing properties of the liquid polybutadiene will deteriorate; if the molecular weight distribution of the liquid polybutadiene is too broad, the mechanical properties of the liquid styrene butadiene polymer will be reduced.

[0051] Furthermore, the molecular weight distribution index (M w / M n ) is 1.21-1.53, preferably 1.26-1.46.

[0052] In the present invention, the liquid polybutadiene has a high 1,2-structural unit content, thereby enabling the liquid polybutadiene to have higher cross-linking activity when used as a cross-linking curing material, thereby facilitating the preparation of a polymer coating with a higher cross-linking density.

[0053] Furthermore, based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is greater than 87 weight %, preferably greater than 89 weight %.

[0054] Furthermore, the molar ratio of cis-1,4-structural units to trans-1,4-structural units in the liquid polybutadiene is 1.3-1.9:1, preferably 1.65-1.75:1.

[0055] In the present invention, when the dynamic viscosity of the liquid polybutadiene at 45° C. is too low, the liquid polybutadiene is easy to flow during processing, while when the dynamic viscosity is too high, the liquid polybutadiene is not easy to apply during processing and has poor uniformity. When the dynamic viscosity of the liquid polybutadiene at 45° C. meets the above range, the liquid polybutadiene can have good fluidity, making the liquid polybutadiene particularly suitable for coatings and adhesives.

[0056] Furthermore, the dynamic viscosity of the liquid polybutadiene at 45° C. is 110-420P, preferably 120-400P, and more preferably 150-300P.

[0057] According to the present invention, based on the total weight of the liquid polybutadiene, the weight content of the metal elements in the liquid polybutadiene is less than 200 ppm.

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

[0059] In the present invention, the content of metal elements in liquid polybutadiene is determined by a plasma method. The specific testing method is as follows: an Optima 8300 full-spectrum direct-reading ICP spectrometer produced by PerkinElmer (PE) of the United States is used, equipped with an echelle grating, a solid-state detector, and dual-solid-state detectors with dual optical paths in the ultraviolet light region and the visible light region, and flat-panel plasma technology is used; the instrument operating parameters are as follows: high-frequency power of 1300 W, plasma gas flow rate of 15 L / min, atomizing gas flow rate of 0.55 L / min, auxiliary gas flow rate of 0.2 L / min, peristaltic pump speed of 1.50 mL / min, integration time of 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, add 5 mL of 10 volume % dilute nitric acid, and slowly heat it 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.

[0060] Furthermore, the metal ion content of the liquid polybutadiene is 100 ppm or less, preferably 50 ppm or less, and more preferably 20 ppm or less.

[0061] According to the present invention, the glass transition temperature (Tg) of the liquid polybutadiene is -35°C to -15°C.

[0062] In the present invention, when the glass transition temperature of the liquid polybutadiene satisfies the above range, the liquid polybutadiene has better heat resistance.

[0063] In the present invention, the glass transition temperature is measured by differential scanning calorimetry. The specific test method is: using a TA-2980DSC differential scanning calorimeter according to the method specified in "GB / T 29611-2013 Raw rubber, Glass transition temperature", the temperature is measured at a heating rate of 20°C / min.

[0064] Furthermore, the glass transition temperature of the liquid polybutadiene is -32°C to -18°C, preferably -30°C to -20°C.

[0065] A second aspect of the present invention provides a method for preparing liquid polybutadiene, characterized in that the method comprises the following steps:

[0066] Under anionic polymerization conditions, 1,3-butadiene 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 polybutadiene;

[0067] Wherein, the temperature of the contact reaction is below 20°C;

[0068] The structure regulator contains component A and component B, wherein component A is selected from ether compounds and / or amine compounds; and component B is selected from alkali metal alcoholates.

[0069] The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-12:1000;

[0070] 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;

[0071] The amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid polybutadiene is 1500-4500.

[0072] The present invention, using the above-mentioned preparation method, can produce liquid polybutadiene having not only a high vinyl content but also a moderate molecular weight distribution, and having a suitable molecular weight and dynamic viscosity. As a result, the liquid polybutadiene has good flow properties, film-forming properties, and coating properties, making it particularly suitable for forming polymer coatings.

[0073] 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;

[0074]

[0075] In formula I, R1 and R2 are the same or different and are independently a hydrogen atom or a C1-C6 alkyl group, R3 and R4 are the same or different and are independently a C1-C6 alkyl group,

[0076] n is an integer from 1 to 5;

[0077]

[0078] In formula II, R5 and R6 are the same or different and are independently a hydrogen atom or a C1-C6 alkyl group,

[0079] 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 are the same or different, and are each independently a hydrogen atom or a C1-C6 alkyl group, and m is an integer of 1-5.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] According to the present invention, 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.

[0085] According to the present invention, the alkali metal alkoxide is a compound represented by formula III;

[0086] R 17 -OM Formula III

[0087] In formula III, R 17 C1-C 20 Alkyl, C6-C 30 Aryl or C4-C 20 The cycloalkyl group,

[0088] M is an alkali metal atom.

[0089] 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.

[0090] 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.

[0091] Furthermore, in Formula III, R 17 C2-C 10 Alkyl or C6-C 12 M can be Li, Na or K, preferably Na.

[0092] 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.

[0093] 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 as lithium.

[0094] 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.

[0095] According to the present invention, the molar ratio of the component B to the component A is 0.4-1.5:1, preferably 0.5-1:1.

[0096] According to the present invention, in order to further control the molecular weight distribution of the liquid polybutadiene so that the obtained liquid polybutadiene has a wide molecular weight distribution, preferably, the weight ratio of the 1,2-butadiene to the 1,3-butadiene is 4-10:1000.

[0097] According to the present invention, the amount of the organolithium initiator is such that the number average molecular weight of the prepared liquid butadiene is 1800-4000, preferably 2000-3800. The method of determining the specific amount of the organolithium initiator based on the expected molecular weight of the polymer is well known to those skilled in the art and will not be described in detail herein.

[0098] According to the present invention, the organic lithium initiator is an organic monolithium compound, preferably 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-C 14 Arylalkyl 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 14Specific 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 1,3-butadiene content (i.e., monomer content) may be 1-15% by weight, preferably 4-14% by weight, and more preferably 6-12% by weight, based on the total amount of the polymerization solvent and 1,3-butadiene. In the present invention, monomer content refers to the weight percentage of 1,3-butadiene determined based on the total amount of the polymerization solvent and 1,3-butadiene 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. More preferably, 1,3-butadiene is contacted with the structure regulator and the organolithium initiator 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 includes: removing at least some of the metal ions in the polymerization reaction mixture obtained by the contact reaction to obtain the liquid polybutadiene. Specifically, the polymerization reaction mixture can be washed to remove at least some of the metal ions.

[0112] In a preferred embodiment of the present invention, the method for removing at least a portion of the metal ions in the polymerization mixture comprises: mixing the polymerization mixture obtained by the contact reaction with a washing liquid, and separating the mixture to separate the oil phase from the mixture to obtain the liquid polybutadiene. 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 mixture and water and / or adding dry ice to the polymerization 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 polybutadiene product;

[0115] S2. Mixing and separating the crude liquid polybutadiene 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 liquid polybutadiene.

[0116] In a preferred embodiment of the present invention, the weight ratio of the first washing liquid to 1,3-butadiene 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 0.3-1.1:1.

[0117] In a preferred embodiment of the present invention, the weight ratio of the second washing liquid to 1,3-butadiene 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 polybutadiene prepared by the above preparation method.

[0119] The liquid polybutadiene prepared by the above-described preparation method has a high vinyl content, a moderate molecular weight distribution, and suitable molecular weight and dynamic viscosity. As a result, the liquid polybutadiene exhibits good flowability, film-forming properties, and coating properties. In particular, coatings formed from the coatings containing the liquid polybutadiene exhibit excellent adhesion to substrates.

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

[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 liquid polybutadiene, 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 polybutadiene or the above-mentioned composition.

[0123] In the present invention, the polymer coating containing the liquid polybutadiene or the composition has high adhesion to the substrate.

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

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

[0127] The present invention will be described in detail below with reference to the embodiments, but the scope of the present invention is not limited thereby.

[0128] Unless otherwise specified, normal temperature and room temperature both mean 25±3°C.

[0129] In the following examples and comparative examples, the 1,2-structural unit content, 1,4-structural unit content, cis-1,4-structural unit content, and trans-1,4-structural unit content of the liquid polybutadiene 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 polybutadiene were determined by gel permeation chromatography analysis using an HLC-8320 gel permeation chromatograph manufactured by Tosoh Corporation of Japan. The chromatographic column was TSKgel Super Multipore HZ-N, the standard column was TSKgel Super Multipore HZ, 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 having a mass 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.

[0131] In the following examples and comparative examples, the glass transition temperature of liquid polybutadiene was measured using a TA-2980 DSC differential scanning calorimeter according to the method specified in GB / T 29611-2013 Raw rubber, glass transition temperature, at a heating rate of 20°C / min.

[0132] In the following examples and comparative examples, the content of metal elements in liquid polybutadiene was determined by a plasma method. The specific test method was as follows: an Optima 8300 full-spectrum direct-reading ICP spectrometer from PerkinElmer (PE) of the United States was used, equipped with an echelle grating, a solid-state detector, a dual-path dual solid-state detector in the ultraviolet and visible light regions, and 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.

[0133] In the following examples and comparative examples, the dynamic viscosity of liquid polybutadiene at 45°C was measured using the capillary method specified in GBT10247-2008, using an Ubbelohde viscometer with a size of 4B at a temperature of 45°C.

[0134] The following chemical reagents are involved in the following examples and comparative examples:

[0135] Antioxidant 264, antioxidant 168, and antioxidant 1076 were purchased from Sinopharm Reagent Company;

[0136] Cyclohexane: purchased from Sinopharm Reagent Company, purity >99.9%, soaked in molecular weight sieve for 15 days, water content less than 5ppm (weight content);

[0137] 1,3-Butadiene: 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] Diethylene glycol dibutyl ether: purchased from J&K Reagent Co., analytical grade;

[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 example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0150] (1) Under nitrogen protection, cyclohexane, structure regulator A, structure regulator B, 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 polymerization reaction mixture containing polybutadiene.

[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 polybutadiene.

[0152] (3) Water was added to the crude liquid polybutadiene obtained in step (2), and carbon dioxide gas was introduced with stirring (the specific amounts of water and carbon dioxide are listed in Table 2). The mixture was then allowed to stand for stratification to separate the aqueous phase. The resulting oil phase was subjected to reduced pressure distillation, and an antioxidant (the specific amount and type are listed in Table 2) was added to the distillation residue to obtain a composition PB1 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0153] Examples 2-7

[0154] Examples 2-7 are used to illustrate the liquid polybutadiene and the preparation method thereof of the present invention.

[0155] Examples 2-7 were prepared using the same method as Example 1, except that compositions PB2-PB7 containing the liquid polybutadiene according to the present invention were prepared under the conditions listed in Table 1. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0156] Example 8

[0157] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0158] Liquid polybutadiene was prepared by the same method as in Example 1, except that the amount of water used in step (2) was 200 g, to obtain a composition PB8 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0159] Example 9

[0160] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0161] Liquid polybutadiene was prepared by the same method as in Example 1, except that the amount of sulfuric acid used in step (2) was 30 mmol, to obtain a composition PB9 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0162] Example 10

[0163] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0164] Liquid polybutadiene was prepared by the same method as in Example 1, except that step (3) was not performed, to obtain a composition PB10 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0165] Example 11

[0166] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0167] Liquid polybutadiene was prepared by the same method as in Example 1, except that the acid used in step (2) was nitric acid, and H +The molar amount of nitric acid was calculated to be the same as the molar amount of sulfuric acid in Example 1, to obtain a composition PB11 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0168] Example 12

[0169] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0170] Liquid polybutadiene was prepared by the same method as in Example 1, except that the structure regulator A in step (1) was diethylene glycol diethyl ether, to obtain a composition PB12 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0171] Example 13

[0172] This example is used to illustrate the liquid polybutadiene and its preparation method of the present invention.

[0173] Liquid polybutadiene was prepared by the same method as in Example 1, except that the structure regulator A in step (1) was diethylene glycol dibutyl ether, to obtain a composition PB13 containing the liquid polybutadiene according to the present invention. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0174] Comparative Example 1

[0175] Liquid polybutadiene 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, to obtain a composition DPB1 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0176] Comparative Example 2

[0177] Liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the structure regulator B, sodium tert-pentoxide, was not used, but only the structure regulator A, diethylene glycol dimethyl ether, was used to obtain a composition DPB2 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0178] Comparative Example 3

[0179] Liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the polymerization reaction temperature was 50° C., to obtain a composition DPB3 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0180] Comparative Example 4

[0181] Liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the polymerization reaction temperature was 50° C., and the structure regulator B, sodium tert-pentoxide, was not used, but only diethylene glycol dimethyl ether was used as the structure regulator A, to obtain a composition DPB4 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0182] Comparative Example 5

[0183] Liquid polybutadiene was prepared by the same method as in Example 1, except that 4 g of 1,2-butadiene was added to obtain a composition DPB5 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0184] Comparative Example 6

[0185] Liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the solvent was tetrahydrofuran in an amount of 2300 g, the initiator was sodium naphthalene in an amount of 85 mmol, and diethylene glycol dimethyl ether and sodium tert-amyloxide were not added to obtain a composition DPB6 containing polybutadiene. The structural property parameters of the prepared polybutadiene are listed in Table 3.

[0186] Comparative Example 7

[0187] Liquid polybutadiene 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, to obtain a composition DPB7 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0188] Comparative Example 8

[0189] Liquid polybutadiene 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, to obtain a composition DPB8 containing liquid polybutadiene. The structural property parameters of the prepared liquid polybutadiene are listed in Table 3.

[0190] Table 1

[0191] Example 1 2 3 4 5 6 7 Type of polymerization solvent Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Cyclohexane Polymerization solvent dosage / g 2300 2300 2300 2300 2300 2300 2300 1,3-Butadiene dosage / g 250 250 250 250 250 250 250 1,2-Butadiene dosage / g 1.7 1.7 1.7 1.5 2 1 2.5 n-Butyl lithium dosage / mmol 85 110 75 65 130 60 150 Structural Modifier A 2G 2G 2G 2G DPE 2G DPE Structure regulator A / g 2 2.5 1.8 1.5 3 1.2 3 Structural Modifier B STA STA STA STA SEO STA STA Structure modifier B / mmol 9 11 8 7 13 6 10 Polymerization reaction temperature 0℃ 0℃ 0℃ 3℃ 6℃ 3℃ 8℃ Polymerization reaction pressure 0.3MPa 0.3MPa 0.3MPa 0.3MPa 0.3MPa 0.3MPa 0.3MPa Polymerization reaction time 90 minutes 90 minutes 90 minutes 80 minutes 70 minutes 80 minutes 70 minutes

[0192] Table 1 (Continued)

[0193] Example 1 12 13 Type of polymerization solvent Cyclohexane Cyclohexane Cyclohexane Polymerization solvent dosage / g 2300 2300 2300 1,3-Butadiene dosage / g 250 250 250 1,2-Butadiene dosage / g 1.7 1.7 1.7 n-Butyl lithium dosage / mmol 85 85 85 Structural Modifier A 2G Diethylene glycol diethyl ether Diethylene glycol dibutyl ether Structure regulator A / g 2 2 2 Structural Modifier B STA STA STA Structure modifier B / mmol 9 9 9 Polymerization reaction temperature 0℃ 0℃ 0℃ Polymerization reaction pressure 0.3MPa 0.3MPa 0.3MPa Polymerization reaction time 90 minutes 90 minutes 90 minutes

[0194] Table 2

[0195]

[0196]

[0197] Table 3

[0198]

[0199] 1 : Based on the total amount of polybutadiene, the content of 1,2-structural units

[0200] 2 : Based on the total amount of polybutadiene, the content of cis-1,4-structural units

[0201] 3 : Based on the total amount of polybutadiene, the content of trans-1,4-structural units

[0202] 4 and 5 :Japan Soda liquid polybutadiene products

[0203] Test Case

[0204] The compositions prepared in Examples 1 to 13 were uniformly coated on the surface of a copper foil with a coating thickness of 0.6 mm. The compositions were cross-linked and cured at 120° C. for 2 hours. The peel strength was measured using the method specified in IPC-TM-6502.4.08C. The experimental results are listed in Table 4.

[0205] Test comparison

[0206] The peel strength of the compositions prepared in Comparative Examples 1-4 and 7-15, as well as B3000 and B2000, was measured using the same method as in the test example. The experimental results are listed in Table 4.

[0207] Table 4

[0208]

[0209]

[0210] As can be seen from Tables 3 and 4, the liquid polybutadiene according to 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, exhibiting good flow properties, coating properties, and film-forming properties. The polymer coating formed after crosslinking and curing has strong adhesion to the substrate. However, the liquid polybutadiene prepared in Comparative Example 7 has a high dynamic viscosity, while the liquid polybutadiene prepared in Comparative Example 8 has a low dynamic viscosity. Both exhibit poor coating and film-forming properties, making it difficult to form a polymer coating with uniform thickness and uniform properties.

[0211] In addition, the liquid polybutadiene according to the present invention has a low metal ion content. The liquid polybutadiene according to the present invention is suitable as a crosslinking agent, adhesive or electrical insulation material.

[0212] 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 polybutadiene, characterized in that The liquid polybutadiene has the following characteristics: (1) The number average molecular weight of the liquid polybutadiene is 1500-4500; (2) the molecular weight distribution index of the liquid polybutadiene is 1.21-1.59; (3) Based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight; (4) The molar ratio of cis-1,4-structural units to trans-1,4-structural units in the liquid polybutadiene is 1-2:1; (5) The dynamic viscosity of the liquid polybutadiene at 45°C is 100-500P.

2. The liquid polybutadiene according to claim 1, wherein The number average molecular weight of the liquid polybutadiene is 1800-4000.

3. The liquid polybutadiene according to claim 2, wherein The number average molecular weight of the liquid polybutadiene is 2000-3800.

4. The liquid polybutadiene according to claim 1 or 2, wherein The molecular weight distribution index of the liquid polybutadiene is 1.21-1.

53.

5. The liquid polybutadiene according to claim 4, wherein The molecular weight distribution index of the liquid polybutadiene is 1.26-1.

46.

6. The liquid polybutadiene according to claim 1 or 2, wherein Based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is greater than 87 weight percent.

7. The liquid polybutadiene according to claim 6, wherein Based on the total weight of the liquid polybutadiene, the content of 1,2-structural units in the liquid polybutadiene is greater than 89 weight percent.

8. The liquid polybutadiene according to claim 1 or 2, wherein The molar ratio of cis-1,4-structural units to trans-1,4-structural units in the liquid polybutadiene is 1.3-1.9:

1.

9. The liquid polybutadiene according to claim 8, wherein The molar ratio of the cis-1,4-structural unit to the trans-1,4-structural unit in the liquid polybutadiene is 1.65-1.75:

1.

10. The liquid polybutadiene according to claim 1 or 2, wherein The dynamic viscosity of the liquid polybutadiene at 45° C. is 120-400P.

11. The liquid polybutadiene according to claim 1 or 2, wherein The dynamic viscosity of the liquid polybutadiene at 45° C. is 150-300P.

12. The liquid polybutadiene according to claim 1 or 2, wherein Based on the total weight of the liquid polybutadiene, the weight content of the metal elements in the liquid polybutadiene is less than 200 ppm.

13. The liquid polybutadiene according to claim 12, wherein Based on the total weight of the liquid polybutadiene, the weight content of the metal elements in the liquid polybutadiene is less than 100 ppm.

14. The liquid polybutadiene according to claim 13, wherein Based on the total weight of the liquid polybutadiene, the weight content of the metal elements in the liquid polybutadiene is less than 50 ppm.

15. The liquid polybutadiene according to claim 14, wherein Based on the total weight of the liquid polybutadiene, the weight content of the metal elements in the liquid polybutadiene is less than 20 ppm.

16. The liquid polybutadiene according to claim 1, wherein The liquid polybutadiene has a glass transition temperature of -35°C to -15°C.

17. The liquid polybutadiene according to claim 16, wherein The glass transition temperature of the liquid polybutadiene is -32°C to -18°C.

18. A method for preparing liquid polybutadiene, characterized in that: The method comprises the following steps: Under anionic polymerization conditions, 1,3-butadiene 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 polybutadiene; Wherein, the temperature of the contact reaction is below 20°C; The structure regulator contains component A and component B, wherein component A is selected from ether compounds and / or amine compounds; and component B is selected from alkali metal alcoholates. The weight ratio of the 1,2-butadiene monomer to the 1,3-butadiene monomer is 2-12:1000; 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 polybutadiene is 1500-4500.

19. The preparation method according to claim 18, wherein The component A is selected from the compound represented by formula I and / or the compound represented by formula II; 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; 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.

20. The preparation method according to claim 18 or 19, 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.

21. The preparation method according to claim 18, wherein The alkali metal alkoxide is a compound represented by formula III; R 17 -OM Formula III In formula III, R 17 C1-C 20 Alkyl, C6-C 30 Aryl or C4-C 20 The cycloalkyl group, M is an alkali metal atom.

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

23. The preparation method according to claim 18, 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.

24. The preparation method according to claim 18, wherein The molar ratio of the component B to the component A is 0.4-1.5:

1.

25. The preparation method according to claim 24, wherein The molar ratio of the component B to the component A is 0.5-1:

1.

26. The preparation method according to claim 18, wherein The weight ratio of the 1,2-butadiene to the 1,3-butadiene is 4-10:1000.

27. The preparation method according to claim 18, wherein The amount of the organic lithium initiator used is such that the number average molecular weight of the prepared liquid butadiene is 1800-4000.

28. The preparation method according to claim 27, wherein The amount of the organic lithium initiator used is such that the number average molecular weight of the prepared liquid butadiene is 2000-3800.

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

30. The preparation method according to claim 18, wherein The organic lithium initiator is selected from n-butyl lithium and / or sec-butyl lithium.

31. The preparation method according to claim 18, wherein The content of 1,3-butadiene is 1-15% by weight based on the total amount of the polymerization solvent and 1,3-butadiene.

32. The preparation method according to claim 31, wherein Based on the total amount of the polymerization solvent and 1,3-butadiene, the content of the 1,3-butadiene is 4-14% by weight.

33. The method of claim 18, wherein: The temperature of the contact reaction is -10°C to 20°C.

34. The method according to claim 33, wherein The temperature of the contact reaction is -5°C to 10°C.

35. The preparation method according to claim 18, wherein The preparation method comprises: removing at least part of the metal ions in the polymerization reaction mixture obtained by the contact reaction to obtain the liquid polybutadiene.

36. The preparation method according to claim 35, 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 polybutadiene.

37. The preparation method according to claim 36, wherein The washing liquid is water or an aqueous solution containing acid.

38. The preparation method according to claim 37, wherein The washing liquid includes a first washing liquid and a second washing liquid.

39. The preparation method according to claim 38, 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.

40. The preparation method according to claim 18, wherein The preparation method comprises: S1, mixing and separating a polymerization reaction mixture obtained by a 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 polybutadiene product; S2. Mixing and separating the crude liquid polybutadiene 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 polybutadiene.

41. The preparation method according to claim 40, wherein The weight ratio of the first washing liquid to the 1,3-butadiene monomer is 0.5-5:

1.

42. The preparation method according to claim 40, 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.

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

1.

44. The preparation method according to claim 40, 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.

45. Liquid polybutadiene obtained by the preparation method according to any one of claims 18 to 44.

46. ​​A composition characterized in that The composition contains liquid polybutadiene and at least one additive, wherein the liquid polybutadiene is the liquid polybutadiene according to any one of claims 1 to 17 and 45; The additives include antioxidants.

47. A polymer coating, characterized in that The polymer coating comprises the liquid polybutadiene according to any one of claims 1 to 17 and 45, or the composition according to claim 46.

48. An adhesive, characterized in that The adhesive contains the liquid polybutadiene according to any one of claims 1 to 17 and 45, or the composition according to claim 46.

49. A cross-linking agent, characterized in that The cross-linking agent comprises the liquid polybutadiene according to any one of claims 1 to 17 and 45, or the composition according to claim 46.

50. Use of the liquid polybutadiene according to any one of claims 1 to 17 and 45, or the composition according to claim 46 as a cross-linking agent, adhesive or electrical insulating material.

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