WO2021232678A1 - 液体聚丁二烯及其制备方法和应用以及组合物和聚合物涂层和胶粘剂和交联剂 - Google Patents

液体聚丁二烯及其制备方法和应用以及组合物和聚合物涂层和胶粘剂和交联剂 Download PDF

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WO2021232678A1
WO2021232678A1 PCT/CN2020/124445 CN2020124445W WO2021232678A1 WO 2021232678 A1 WO2021232678 A1 WO 2021232678A1 CN 2020124445 W CN2020124445 W CN 2020124445W WO 2021232678 A1 WO2021232678 A1 WO 2021232678A1
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liquid polybutadiene
polybutadiene
liquid
present
molecular weight
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English (en)
French (fr)
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李建成
徐林
王雪
邵明波
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to KR1020227045027A priority Critical patent/KR102848140B1/ko
Priority to CA3183999A priority patent/CA3183999A1/en
Priority to JP2022571236A priority patent/JP7571158B2/ja
Priority to US17/999,281 priority patent/US12516183B2/en
Priority to BR112022023648-4A priority patent/BR112022023648B1/pt
Priority to EP20936962.8A priority patent/EP4148072A4/en
Publication of WO2021232678A1 publication Critical patent/WO2021232678A1/zh
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/56—Alkali metals being the only metals present, e.g. Alfin catalysts
    • C08F4/565—Lithium being present, e.g. butyllithium + sodiumphenoxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C

Definitions

  • the invention relates to a liquid polybutadiene and its preparation method and application; the invention also relates to a composition containing the liquid polybutadiene; the invention further relates to a liquid polybutadiene and the composition Of polymer coatings, adhesives and crosslinking agents.
  • Liquid polybutadiene is a viscous flowable polymer with a number average molecular weight of 500-10000. It is an oily liquid at room temperature. It has a wide range of uses in coatings, inks, surfactants and polymer modifiers. .
  • liquid polybutadiene can be divided into 1,4-addition (cis and trans isomers) and 1,2-addition products.
  • 1,2-addition products according to ethylene
  • the content of base can be divided into medium vinyl liquid polybutadiene and high vinyl liquid polybutadiene.
  • 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, but The above catalyst system has the following shortcomings: (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 and has poor weather resistance.
  • the purpose of the present invention is to provide a liquid polybutadiene, which not only has a high vinyl content, but also has a narrow molecular weight distribution, and at the same time has a suitable molecular weight and dynamic viscosity.
  • the present invention provides a liquid polybutadiene, the number average molecular weight of the liquid polybutadiene is 2500-5500, the molecular weight distribution index is 1-1.2, and the liquid polybutadiene Based on the total amount of olefins, the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight, and the content of 1,4-structural units in the liquid polybutadiene is 5-15% by weight
  • the molar ratio of the cis 1,4-structural unit to the trans 1,4-structural unit in the liquid polybutadiene is 1-2:1, and the dynamic viscosity of the liquid polybutadiene at 45°C is 100- 500P.
  • the present invention provides a method for preparing liquid polybutadiene, the method comprising: under anionic polymerization conditions, 1,3-butadiene and structure regulator and organolithium
  • the initiator is contacted in the polymerization solvent to obtain a polymerization reaction mixture containing polybutadiene.
  • the contact is carried out at a temperature of -10°C to 20°C.
  • the structure modifier contains component A and component B.
  • the component A is one or two or more selected from ethers and amines
  • the component B is one or two or more selected from alkali metal alkoxides
  • organolithium initiator component A: group
  • the molar ratio of Part B is 1:0.05-0.3:0.03-0.2, and the organic lithium initiator is calculated as lithium;
  • the component A is one or two or more selected from the compound represented by formula I and the compound represented by formula II,
  • R 1 and R 2 are the same or different, and are each independently a hydrogen atom or a C 1 -C 6 alkyl group,
  • R 3 and R 4 are the same or different, and are each independently a C 1 -C 6 alkyl group
  • n is an integer of 1-5;
  • R 5 and R 6 are the same or different, and are each independently a hydrogen atom or a C 1 -C 6 alkyl group,
  • R 7 and R 8 are the same or different, each independently a C 1 -C 6 alkylene group
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are the same or different
  • Each independently is a hydrogen atom or a C 1 -C 6 alkyl group
  • n is an integer of 1-5.
  • the present invention provides a liquid polybutadiene prepared by the method according to the second aspect of the present invention.
  • the present invention provides a composition containing liquid polybutadiene and at least one additive.
  • the liquid polybutadiene is the first or third aspect of the present invention.
  • the present invention provides a polymer coating containing the liquid polybutadiene according to the first aspect or the third aspect of the present invention, or the third aspect of the present invention.
  • the present invention provides an adhesive containing the liquid polybutadiene described in the first or third aspect of the present invention, or the liquid polybutadiene described in the fourth aspect of the present invention combination.
  • the present invention provides a crosslinking agent containing the liquid polybutadiene according to the first aspect or the third aspect of the present invention, or the fourth aspect of the present invention The composition.
  • the present invention provides the liquid polybutadiene according to the first or third aspect of the present invention, or the composition according to the fourth aspect of the present invention as cross-linking
  • the liquid polybutadiene according to the present invention not only has a relatively high vinyl content, but also has a narrow molecular weight distribution, and at the same time has a suitable molecular weight and dynamic viscosity.
  • the liquid polybutadiene according to the present invention has good flow properties, good film-forming properties and coating properties, and is particularly suitable for forming polymer coatings, and the formed polymer coatings have improved adhesion to the substrate.
  • the liquid polybutadiene according to the present invention has good application prospects in the fields of crosslinking agents, adhesives and electrical insulating materials.
  • liquid polybutadiene refers to polybutadiene having fluidity at a temperature of 25°C.
  • the present invention provides a liquid polybutadiene, the number average molecular weight of the liquid polybutadiene is 2500-5500, the molecular weight distribution index is 1-1.2, and the liquid polybutadiene Based on the total amount of olefins, the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight, and the content of 1,4-structural units in the liquid polybutadiene is 5-15% by weight
  • the molar ratio of the cis 1,4-structural unit to the trans 1,4-structural unit in the liquid polybutadiene is 1-2:1, and the dynamic viscosity of the liquid polybutadiene at 45°C is 100- 500P.
  • the liquid polybutadiene of the present invention has a number average molecular weight (M n) of 2500-5500.
  • M n number average molecular weight
  • the number average molecular weight of the liquid polybutadiene is 2800-5000. More preferably, the number average molecular weight of the liquid polybutadiene is 3000-4500.
  • the molecular weight distribution index (M w /M n ) of the liquid polybutadiene is 1-1.2.
  • the molecular weight distribution index of the liquid polybutadiene is preferably 1.01-1.09, more preferably 1.02-1.06.
  • the molecular weight and molecular weight distribution index of liquid polybutadiene are analyzed and determined by gel permeation chromatography, and the gel permeation chromatography analysis adopts the HLC-8320 gel permeation chromatograph of Tosoh Corporation, Japan, and the chromatographic column is TSKgel SuperMultiporeHZ- N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure tetrahydrofuran (THF), and narrow-distributed polystyrene is used as the standard sample.
  • the polymer sample is prepared into a tetrahydrofuran solution with a mass concentration of 1 mg/mL, and the injection volume is 10.00 ⁇ L.
  • the flow rate is 0.35 mL/min, and the test temperature is 40.0°C.
  • the content of 1,2-structural units in the liquid polybutadiene is 85-95% by weight.
  • the content of 1,2-structural units in the liquid polybutadiene is 87% by weight or more, for example, it can be 87-94% by weight.
  • the content of 1,2-structural units in the liquid polybutadiene is 90% by weight or more, preferably 90-93% by weight, such as 90, 90.1 , 90.2, 90.3, 90.4, 90.5, 90.6, 90.7, 90.8, 90.9, 91, 91.1, 91.2, 91.3, 91.4, 91.5, 91.6, 91.7, 91.8, 91.9, 92, 92.1, 92.2, 92.3, 92.4, 92.5, 92.6 , 92.7, 92.8, 92.9 or 93% by weight.
  • the content of 1,4-structural units in the liquid polybutadiene is 5-15% by weight.
  • the molar ratio of the cis 1,4-structural unit to the trans 1,4-structural unit in the liquid polybutadiene is 1-2:1, preferably 1.3-1.9:1.
  • the molar ratio of the trans 1,4-structural unit to the cis 1,4-structural unit in the liquid polybutadiene is 1.65-1.75:1.
  • the polymer coating formed by the liquid polybutadiene according to this preferred example has higher adhesion to the substrate and exhibits higher peel strength.
  • 1,2-structural unit refers to the structural unit formed by the 1,2-polymerization of butadiene, and the content of the 1,2-structural unit can also be referred to as the vinyl content; in the present invention, The term “1,4-structural unit” refers to a structural unit formed by 1,4-polymerization of butadiene.
  • cis 1,4-structural unit refers to a structural unit formed by 1,4-polymerization of butadiene and having a cis configuration, that is, the structural unit represented by the following formula:
  • trans 1,4-structural unit refers to the structural unit of butadiene formed by 1,4-polymerization and the configuration is trans, that is, the structural unit represented by the following formula:
  • 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 test method is: Bruker AVANCE400 superconducting nuclear magnetic resonance wave instrument test, 1 H nuclear resonance frequency is 300.13MHz, spectral width is 2747.253Hz, pulse width is 5.0 ⁇ s, data point is 16K, sample tube diameter is 5mm, solvent is deuterated chloroform ( CDCl 3 ), the sample concentration is 15 mg/mL, the test temperature is normal temperature, the number of scans is 16 times, and the tetramethylsilane chemical shift is 0 ppm for calibration.
  • the liquid polybutadiene of the present invention has a dynamic viscosity of 100-500 poise (P) at 45° C., has good fluidity, and is particularly suitable for coatings and adhesives.
  • the liquid polybutadiene according to the present invention has a dynamic viscosity of 150-350P at 45°C. More preferably, the liquid polybutadiene according to the present invention has a dynamic viscosity of 170-300P at 45°C. Further preferably, the liquid polybutadiene according to the present invention has a dynamic viscosity of 180-250P at 45°C.
  • the dynamic viscosity of the liquid polybutadiene according to the present invention does not change much with the molecular weight, and can show a suitable dynamic viscosity in a wide range.
  • the number average molecular weight of the liquid polybutadiene is 2500-4000, preferably 3000-4000, and the power of the liquid polybutadiene at 45°C is
  • the viscosity is 100-280P, preferably 150-260P.
  • the molecular weight distribution index of the liquid polybutadiene may be 1-1.05.
  • the number average molecular weight of the liquid polybutadiene is greater than 4000 and not greater than 5500, and the dynamic viscosity of the liquid polybutadiene at 45°C is More than 280P and not more than 500P, preferably 280-480P.
  • the molecular weight distribution index of the liquid polybutadiene may be 1-1.08.
  • the dynamic viscosity is measured with reference to the capillary method specified in GBT10247-2008, in which the Ubbelohde viscometer with size number 4B is used for measurement at a temperature of 45°C.
  • the glass transition temperature (T g ) of the liquid polybutadiene is -32°C to -12°C, preferably -29°C to -15°C, more preferably -27°C To -17°C.
  • the glass transition temperature is measured by differential scanning calorimetry.
  • the specific test method is: TA-2980DSC differential scanning calorimeter is used in accordance with "GB/T 29611-2013 raw rubber, glass transition temperature”. Measured by the method, the heating rate is 20°C/min.
  • the weight content of metal elements in the liquid polybutadiene may be 200 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less , More preferably, it is 20 ppm or less.
  • the content of metal elements in liquid polybutadiene is determined by plasma method, and the specific test method is: adopting PerkinElmer (PE) company Optima 8300 full-spectrum direct reading ICP spectrometer, equipped with echelle grating , Solid-state detector, dual-light path dual-solid-state detector for ultraviolet and visible regions, using flat plasma technology; instrument operating parameters are as follows: high-frequency power 1300W, plasma gas flow rate 15L/min, atomizing gas flow rate 0.55L/min, The auxiliary gas flow rate is 0.2L/min, the peristaltic pump speed is 1.50mL/min, the integration time is 10s, and the plasma axis is observed.
  • PE PerkinElmer
  • the sample preparation method is as follows: accurately weigh 2.000g of the sample in a porcelain crucible, place it in a high-temperature resistance furnace and gradually raise the temperature to 500°C, take it out after the ashing is complete, add 5mL 10% by volume dilute nitric acid, and slowly heat it on the electric hot plate until Completely dissolved, the solution was evaporated to dryness, 1mL concentrated nitric acid (concentration 68% by volume) was added, transferred to a 50mL volumetric flask, and the volume was made constant with water, and a reagent blank solution was prepared at the same time.
  • the present invention provides a method for preparing liquid polybutadiene, the method comprising: under anionic polymerization conditions, 1,3-butadiene and structure regulator and organolithium The initiator is contacted in the polymerization solvent to obtain a polymerization reaction mixture containing polybutadiene, and the contact is performed at a temperature not higher than 40°C.
  • the structure modifier contains component A and component B, and the component A is one or two or more selected from ethers and amines, and the component B is selected from alkalis. One or two or more of metal alkoxides.
  • the component A is one or two or more selected from the compound represented by formula I and the compound represented by formula II:
  • R 1 and R 2 are the same or different, and are each independently a hydrogen atom or a C 1 -C 6 alkyl group,
  • R 3 and R 4 are the same or different, and are each independently a C 1 -C 6 alkyl group
  • n is an integer of 1-5, for example: 1, 2, 3, 4 or 5;
  • R 5 and R 6 are the same or different, and are each independently a hydrogen atom or a C 1 -C 6 alkyl group,
  • R 7 and R 8 are the same or different, each independently a C 1 -C 6 alkylene group
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are the same or different
  • Each independently is a hydrogen atom or a C 1 -C 6 alkyl group
  • n is an integer of 1-5, and may be 1, 2, 3, 4, or 5, for example.
  • the C 1 -C 6 alkyl group includes a C 1 -C 6 straight chain alkyl group and a C 3 -C 6 branched chain alkyl group. 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.
  • R 1 and R 2 are both hydrogen atoms; R 3 and R 4 are the same and are methyl, ethyl, n-propyl or n-butyl.
  • R 5 and R 6 are both hydrogen atoms
  • R 7 and R 8 are C 2 -C 4 alkylene groups
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are all hydrogen atoms.
  • preferred examples of the component A may include, but are not limited to: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di One or more of n-butyl ether and 1,2-dipiperidinylethane.
  • the alkali metal alkoxide is preferably one or two or more selected from the compounds represented by formula III,
  • R 17 is a C 1 -C 20 alkyl group, a C 6 -C 30 aryl group or a C 4 -C 20 cycloalkyl group, preferably a C 2 -C 10 alkyl group or a C 6 -C Cycloalkyl of 12 , more preferably C 2 -C 6 alkyl;
  • M is an alkali metal atom, and may be Li, Na, or K, for example, and is preferably Na.
  • the C 1 -C 20 alkyl group includes a C 1 -C 20 straight chain alkyl group and a C 3 -C 20 branched chain alkyl group. Specific examples thereof 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 Group and its isomers, tetradecyl and its isomers, pentadecyl and its isomers, hexadecyl and its.
  • C 4 -C 20 cycloalkyl groups include cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-propyl Butylcyclohexyl or 2-isopropyl-5-methylcyclohexyl.
  • alkali metal alkoxide may include, but are not limited to: one of sodium tert-butoxide, sodium tert-pentoxide, sodium menthol, sodium ethoxide, and sodium n-hexanoxide Or two or more.
  • the molar ratio of the organolithium initiator: component A: component B is 1:0.05-0.3:0.03-0.2, and the organolithium initiator is calculated as lithium.
  • the molar ratio of the organolithium initiator: component A: component B is 1:0.08-0.25:0.04-0.18, and the organolithium initiator is calculated as lithium.
  • the molar ratio of the organolithium initiator: component A: component B is 1:0.1-0.2:0.05-0.15, and the organolithium initiator is calculated as lithium.
  • the molar ratio of component B:component A is preferably 0.4-1.5:1, more preferably 0.5-1:1.
  • the organic lithium initiator is preferably an organic monolithium compound, more preferably a compound represented by formula IV,
  • R 18 is a C 1 -C 6 alkyl group, a C 3 -C 12 cycloalkyl group, a C 7 -C 14 aralkyl group, or a C 6 -C 12 aryl group.
  • the C 1 -C 6 alkyl group includes a C 1 -C 6 straight chain alkyl group and a C 3 -C 6 branched chain alkyl group. 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.
  • C 3 -C 12 cycloalkyl group may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-normal Propylcyclohexyl and 4-n-butylcyclohexyl.
  • C 7 -C 14 aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl n-propyl, phenyl n-butyl, phenyl t-butyl, Phenyl isopropyl, phenyl n-pentyl and phenyl n-butyl.
  • C 6 -C 12 aryl group may include, but are not limited to: phenyl, naphthyl, 4-methylphenyl, and 4-ethylphenyl.
  • the organic lithium initiator may include, but are not limited to: ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, and tert-butyl lithium , Phenyl lithium, 2-naphthyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium, and 4-butylcyclohexyl lithium.
  • the organolithium initiator is n-butyl lithium and/or sec-butyl lithium, and more preferably, the organolithium initiator is n-butyl lithium.
  • the amount of the organic lithium initiator can be selected according to the expected molecular weight of the liquid polybutadiene.
  • the amount of the organic lithium initiator is such that the number average molecular weight of the prepared liquid polybutadiene is 2500-5500, preferably 2800-5000, more preferably 3000-4500.
  • the method for determining the specific dosage 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.
  • the polymerization solvent may be various organic substances 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 may be one or two or more selected from cyclohexane, n-hexane, n-pentane, n-heptane, benzene, and raffinate.
  • the raffinate is the distillate remaining after the aromatics are extracted from the aromatics-rich catalytic reforming products in the petroleum refining process.
  • the polymerization solvent can be used alone or in combination.
  • the content of 1,3-butadiene (ie, the monomer content) may be 1-15% by weight, preferably 2-12% by weight, more preferably 4-10% by weight.
  • the monomer content refers to the weight percentage of 1,3-butadiene determined on the basis of the total amount of the polymerization solvent and 1,3-butadiene before the polymerization reaction.
  • 1,3-butadiene is contacted with a structure modifier and an organolithium initiator in a polymerization solvent at a temperature of -10°C to 20°C to carry out anionic polymerization reaction, for example: , 3-butadiene and structure modifier and organolithium initiator at -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, the 1,3-butadiene is contacted with the structure modifier and the organolithium initiator at a temperature not higher than 10
  • 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.
  • the pressure refers to gauge pressure.
  • the time of the anionic polymerization reaction can be selected according to the temperature of the polymerization reaction, and can generally be 30-240 min, preferably 40-120 min.
  • the anionic polymerization reaction is carried out in an atmosphere formed of an inert gas.
  • the inactive gas refers to a gas that does not chemically interact with reactants, reaction products, and solvents under polymerization conditions, such as nitrogen and/or group zero element gas (such as argon).
  • the preparation method may further include: removing at least part of the metal ions in the polymerization reaction mixture to obtain a purified polymerization reaction mixture.
  • the polymerization reaction mixture can be washed to remove at least part of the metal ions.
  • the method for removing at least part of the metal ions in the polymerization reaction mixture includes: mixing the polymerization reaction mixture with a washing liquid, separating the oil phase from the mixture, and the washing liquid It is water or an aqueous solution containing acid.
  • the acid is preferably an inorganic acid, more preferably one or two or more of sulfuric acid, nitric acid, hydrochloric acid, and 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.
  • the washing liquid includes a first washing liquid and a second washing liquid
  • the first washing liquid is an aqueous solution containing acid I
  • the second aqueous solution is containing An aqueous solution of acid II.
  • the acid I is one or more of sulfuric acid, hydrochloric acid and nitric acid
  • the acid II is carbonic acid.
  • the method for removing at least part of the metal ions in the polymerization reaction mixture includes: The polymerization reaction mixture liquid is mixed with the first washing liquid to obtain a first mixture, the first oil phase is separated from the first mixture, and at least part of the polymerization solvent in the first oil phase is removed to obtain a crude liquid polybutadiene Product; in the presence of carbon dioxide, the first oil phase is mixed with water to obtain a second mixture, the second oil phase is separated from the second mixture, and at least part of the volatile components in the second oil phase are removed , To obtain liquid polybutadiene.
  • the weight ratio of the first washing liquid to 1,3-butadiene is preferably 0.5-5:1, more preferably 2-4:1, and the first washing liquid
  • the molar ratio of the acid I to the organolithium initiator is preferably 0.1-1.5:1, more preferably 0.2-1:1, still more preferably 0.3-0.6:1, the acid I is calculated as H + ;
  • the second The weight ratio of washing liquid to 1,3-butadiene is 1-2:1.
  • the molar ratio of the acid II to the organolithium initiator in the second washing liquid is preferably 0.1-1.5:1, more preferably 0.2-1:1, further preferably 0.3-0.6:1, and the acid I is H + meter.
  • the present invention provides a liquid polybutadiene prepared by the method according to the second aspect of the present invention.
  • the liquid polybutadiene prepared by the method described in the second aspect of the present invention not only has a high vinyl content, but also has a narrow molecular weight distribution, as well as a suitable molecular weight and dynamic viscosity.
  • the liquid polybutadiene according to the present invention has good flow properties, good film-forming properties and coating properties, especially the coating formed by the coating containing the liquid polybutadiene of the present invention, has improved adhesion to the substrate. Focus on.
  • the present invention provides a composition containing liquid polybutadiene and at least one additive, wherein the liquid polybutadiene is the first aspect of the present invention.
  • the liquid polybutadiene is the first aspect of the present invention.
  • the additive may be a substance that can impart new properties to the composition and/or improve the existing properties of the composition.
  • the additive contains an antioxidant.
  • the antioxidant may be a conventional choice, for example, the antioxidant may be a phenolic and/or amine antioxidant.
  • the antioxidant may be 4,6-dioctylthiomethyl o-cresol, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (Ie, antioxidant 264), tris(2,4-di-tert-butylphenyl) phosphite (ie, antioxidant 168), 3-(3,5-di-tert-butyl-4-hydroxybenzene) Base) stearyl propionate (ie, antioxidant 1076), 2,6-di-tert-butyl p-cresol, tert-butyl catechol and 2,2'-methylene-bis(4-methyl Yl-6-tert-butylphenol) one kind or two or more kinds.
  • the content of the antioxidant may be 0.005-2 parts by weight, preferably 0.01-1 parts by weight.
  • the present invention provides a polymer coating containing the liquid polybutadiene according to the first or third aspect of the present invention, or the third aspect of the present invention.
  • the polymer coating according to the present invention has high adhesion to the substrate.
  • the present invention provides an adhesive containing the liquid polybutadiene described in the first or third aspect of the present invention, or the liquid polybutadiene described in the fourth aspect of the present invention combination.
  • the present invention provides a crosslinking agent containing the liquid polybutadiene according to the first or third aspect of the present invention, or the fourth aspect of the present invention.
  • the composition of the aspect is not limited to the first or third aspect of the present invention, or the fourth aspect of the present invention.
  • the present invention provides the liquid polybutadiene according to the first or third aspect of the present invention, or the composition according to the fourth aspect of the present invention as a crosslinking agent, Application of adhesives or electrical insulating materials.
  • both room temperature and room temperature indicate 25 ⁇ 3°C.
  • the structural unit content of the liquid 1,2-polybutadiene was measured using a nuclear magnetic resonance instrument Bruker AVANCE400-type superconducting, 1 H nuclear resonance frequency of 300.13 MHz, a spectral width of 2747.253Hz, pulse The width is 5.0 ⁇ s, the data point is 16K, the sample tube diameter is 5mm, the solvent is deuterated chloroform (CDCl 3 ), the sample concentration is 15mg/mL, the test temperature is normal temperature, the number of scans is 16 times, and the chemistry is based on tetramethylsilane. The displacement is calibrated at 0 ppm.
  • the molecular weight and molecular weight distribution index of the liquid polybutadiene are determined by gel permeation chromatography.
  • the gel permeation chromatography is analyzed by the HLC-8320 gel permeation chromatograph of Tosoh Corporation, Japan, with a chromatographic column. It is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure tetrahydrofuran (THF), and narrow-distributed polystyrene is used as the standard sample.
  • the polymer sample is prepared into a tetrahydrofuran solution with a mass concentration of 1 mg/mL.
  • the injection volume It is 10.00 ⁇ L, the flow rate is 0.35mL/min, and the test temperature is 40.0°C.
  • the glass transition temperature of liquid polybutadiene was measured with a TA-2980DSC differential scanning calorimeter in accordance with the method specified in GB/T 29611-2013 raw rubber, glass transition temperature, and the heating rate It is 20°C/min.
  • the content of metal elements in liquid polybutadiene is determined by plasma method.
  • the specific test method is: using PerkinElmer (PE) company Optima 8300 full-spectrum direct reading ICP spectrometer, Equipped with echelle grating, solid-state detector, dual-path dual-solid-state detector for ultraviolet and visible regions, using flat plasma technology; instrument operating parameters are as follows: high-frequency power 1300W, plasma gas flow rate 15L/min, atomization gas flow rate 0.55 L/min, auxiliary gas flow rate 0.2L/min, peristaltic pump speed 1.50mL/min, integration time 10s, plasma axial observation.
  • PE PerkinElmer
  • the sample preparation method is as follows: accurately weigh 2.000g of the sample in a porcelain crucible, place it in a high-temperature resistance furnace and gradually raise the temperature to 500°C, take it out after the ashing is complete, add 5mL 10% (V%) dilute nitric acid, and place it on the electric hot plate. Slowly heat until completely dissolved, the solution is evaporated to dryness, add 1 mL of concentrated nitric acid (concentration 68% by volume), transfer to a 50 mL volumetric flask, and dilute to volume with water, while preparing a reagent blank solution.
  • the dynamic viscosity of liquid polybutadiene at 45°C is measured with reference to the capillary method specified in GBT10247-2008, in which the Ubbelohde viscometer with size 4B is used for measurement at a temperature of 45°C .
  • Antioxidant 264, Antioxidant 168 and Antioxidant 1076 were purchased from Sinopharm Reagent Company;
  • Cyclohexane purchased from Sinopharm Reagent Company, purity>99.9%, molecular weight sieve soaked for 15 days, water content is less than 5ppm (weight content);
  • 1,3-Butadiene polymer grade, purchased from Yanshan Petrochemical;
  • N-Butyl lithium purchased from Bailingwei Reagent Company, as a 1.6 mol/L hexane solution;
  • Diethylene glycol diethyl ether purchased from Bailingwei Reagent Company, analytically pure;
  • Diethylene glycol dibutyl ether purchased from Bailingwei Reagent Company, analytically pure;
  • DPE 1,2-Dipiperidinylethane
  • Sodium tert-pentoxide (STA, molecular weight 110): purchased from Bailingwei Reagent Company, 1.4mol/L tetrahydrofuran solution;
  • Sodium menthol (SMT, molecular weight 178): Provided by Yinuokai Reagent Company, 1.0mol/L tetrahydrofuran solution;
  • TEDA N,N,N’,N’-Tetramethylethylenediamine
  • Methylmorpholine purchased from Sinopharm Reagent Co., Ltd., analytical grade;
  • Sulfuric acid purchased from Bailingwei Reagent Company, with a concentration of 98% by weight, and prepared into a 20% by weight solution with water;
  • Nitric acid purchased from Sinopharm Reagent Company, with a concentration of 68% by weight, and prepared into a 20% by weight solution with water.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • step (2) Add water and acid to the polymerization reaction mixture obtained in step (1) (the specific amount and acid type are listed in Table 2, and the amounts listed in the table are all measured as pure compounds), and after stirring for 15 minutes, proceed Stand for stratification, separate the water phase, and subject the obtained oil phase to vacuum distillation to remove the crude liquid polybutadiene.
  • step (3) Add water to the crude liquid polybutadiene obtained in step (2), and pass in carbon dioxide gas with stirring (the specific amounts of water and carbon dioxide are listed in Table 2), then stand still for stratification, and separate the water phase , The obtained oil phase is subjected to vacuum distillation, and antioxidants are added to the distillation residue (the specific amount and types are listed in Table 2) to obtain the 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.
  • Examples 2-7 are used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • Examples 2-7 used the same method as Example 1 to prepare liquid polybutadiene, except that the composition PB2-PB7 containing the liquid polybutadiene according to the present invention was prepared under the conditions listed in Table 1. Among them, the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the addition amount of n-butyl lithium was 50 mmol, to obtain the composition PB8 containing the liquid polybutadiene according to the present invention, wherein the prepared liquid polybutadiene
  • the structural property parameters of butadiene are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the amount of water in step (2) was 200 g to obtain the composition PB9 containing the liquid polybutadiene according to the present invention, wherein the prepared
  • the structural property parameters of liquid polybutadiene are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the amount of sulfuric acid in step (2) was 30 mmol, to obtain the composition PB10 containing the liquid polybutadiene according to the present invention, wherein the prepared
  • the structural property parameters of liquid polybutadiene are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that step (3) was not performed to obtain the composition PB11 containing the liquid polybutadiene according to the present invention, wherein the prepared liquid polybutadiene
  • the structural property parameters of the alkene are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the acid used in step (2) was nitric acid. Calculated by H + , the molar amount of nitric acid was the same as the molar amount of sulfuric acid in Example 1. , The composition PB12 containing the liquid polybutadiene according to the present invention is obtained, wherein the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the structure modifier 1 in step (1) was diethylene glycol diethyl ether to obtain a composition containing the liquid polybutadiene according to the present invention PB13, in which the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • This example is used to illustrate the liquid polybutadiene of the present invention and its preparation method.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the structure modifier 1 in step (1) was diethylene glycol dibutyl ether to obtain a combination containing the liquid polybutadiene according to the present invention PB14, in which the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the amount of structure modifier 1 diethylene glycol dimethyl ether in step (1) was 0.4 g to obtain a combination containing liquid polybutadiene
  • the structure and property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that the structure regulator 2 sodium tert-pentoxide was not used in step (1), but only the structure regulator 1 diethylene glycol dimethyl Ether to obtain a composition DPB2 containing liquid polybutadiene, wherein the structural property parameters of the prepared liquid polybutadiene are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the polymerization temperature was 50°C to obtain the composition DPB3 containing liquid polybutadiene, wherein the prepared liquid
  • the structural property parameters of polybutadiene are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the temperature of the polymerization reaction was 50°C, and the structure modifier 2 tert-pentoxy sodium was not used, but only Structure modifier 1 diethylene glycol dimethyl ether to obtain the composition DPB4 containing liquid polybutadiene, wherein the structure property parameters of the prepared liquid polybutadiene are listed in Table 3.
  • the polybutadiene was prepared by the same method as in Example 1, except that in step (1), the dosage of n-butyllithium was 3 mmol to obtain the composition DPB5 containing polybutadiene, wherein the prepared polybutadiene
  • the structural property parameters of the alkene are listed in Table 3.
  • the polybutadiene was prepared by the same method as in Example 1, except that in step (1), the amount of n-butyllithium was 3mmol, the amount of diethylene glycol dimethyl ether was 0.08g, and the sodium tert-pentoxide was 0.3 mmol, the composition DPB6 containing polybutadiene is obtained, wherein the structural property parameters of the prepared polybutadiene are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the solvent was tetrahydrofuran, the dosage was 2300g, the initiator was sodium naphthalene, the dosage was 70mmol, and no diethylene glycol was added. Methyl ether and sodium tert-pentoxy to obtain the composition DPB7 containing polybutadiene, wherein the structure and property parameters of the prepared polybutadiene are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the same amount of TMEDA was used instead of diethylene glycol dimethyl ether, and the same amount of SMT was used instead of STA to obtain a liquid
  • the composition DPB8 of polybutadiene, in which the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), TMEDA was used instead of diethylene glycol dimethyl ether and STA was not added to obtain a composition containing liquid polybutadiene DPB9, where the structural property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the same amount of TMEDA was used instead of diethylene glycol dimethyl ether to obtain the composition DPB10 containing liquid polybutadiene , Among them, the structural property parameters of the prepared liquid polybutadiene are listed in Table 3.
  • the liquid polybutadiene was prepared by the same method as in Example 1, except that in step (1), the dosage of n-butyllithium was 125 mmol to obtain the composition DPB11 containing liquid polybutadiene, wherein the prepared
  • the structural property parameters of liquid polybutadiene are listed in Table 3.
  • liquid polybutadiene was prepared by the same method as in Example 7, except that in step (1), 1,2-dipiperidinylethane was replaced with an equivalent amount of methylmorpholine to obtain liquid polybutadiene
  • diene composition DPB15 wherein the structure and property parameters of the liquid polybutadiene prepared are listed in Table 3.
  • Example 14 Using the composition prepared in Example 1 to Example 14, uniformly coat it on the surface of the copper foil with a coating thickness of 0.6mm, cross-linking and curing at 120°C for 2 hours, using IPC-TM-650 2.4.08C The specified method is used to determine the peel strength, and the experimental results are listed in Table 4.
  • the liquid polybutadiene according to the present invention not only has a high content of 1,2-structural units, a narrow molecular weight distribution, but also a moderate molecular weight and a good dynamic viscosity at 45°C. It has good flow properties, coating properties and film-forming properties, and the polymer coating formed after cross-linking and curing has strong adhesion to the substrate.
  • the liquid polybutadiene prepared in Comparative Examples 11, 13 and 14 has low dynamic viscosity, poor coating performance and film-forming performance, and it is difficult to form a polymer coating with uniform thickness and uniform performance.
  • liquid polybutadiene according to the present invention has a low metal ion content.
  • the liquid polybutadiene according to the invention is suitable as a crosslinking agent, adhesive or electrical insulating material.

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Abstract

一种液体聚丁二烯及其制备方法和应用，该液体聚丁二烯的数均分子量为2500-5500，分子量分布指数为1-1.2，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为85-95重量％，该液体聚丁二烯中1,4-结构单元的含量为5-15重量％，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1-2：1，所述液体聚丁二烯在45℃时的动力粘度为100-500P。该液体聚丁二烯具有良好的流动性能，成膜性和涂布性能好，形成的涂层对基材具有提高的附着力。

Description

液体聚丁二烯及其制备方法和应用以及组合物和聚合物涂层和胶粘剂和交联剂
相关申请的交叉引用
本申请要求2020年05月21日提交的中国专利申请202010436914.8的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及一种液体聚丁二烯及其制备方法和应用；本发明还涉及含有所述液体聚丁二烯的组合物；本发明进一步涉及含有所述液体聚丁二烯和所述组合物的聚合物涂层、胶粘剂和交联剂。
背景技术
液体聚丁二烯是一种数均分子量为500-10000的粘稠状可流动聚合物，常温下为油状液体，在涂料、油墨、表面活性剂以及聚合物改性剂等方面具有广泛的用途。
按照微观结构分类，液体聚丁二烯可以分为1,4-加成(顺式和反式异构体)和1,2-加成产物，在1,2-加成产物中，根据乙烯基的含量，可以分为中乙烯基液体聚丁二烯和高乙烯基液体聚丁二烯。
高乙烯基液体聚丁二烯是指1,2-结构含量在65重量％以上的液体聚丁二烯，高乙烯基液体聚丁二烯一般采用铁系、钴系和钼系催化剂制备，但上述催化剂体系存在以下缺点：(1)难以实现低分子量液体聚丁二烯的制备；(2)分子量分布宽，剥离强度低；以及(3)含有变价金属，耐候性差。
因此，有必要开发高乙烯基含量且分子量分布窄的液体聚丁二烯。
发明内容
本发明的目的在于提供一种液体聚丁二烯，该液体聚丁二烯不仅乙烯基含量高，而且分子量分布窄，同时还具有适宜的分子量和动力粘度。
根据本发明的第一个方面，本发明提供了一种液体聚丁二烯，该液体聚丁二烯的数均分子量为2500-5500，分子量分布指数为1-1.2，以该液体聚丁二烯的总量为 基准，该液体聚丁二烯中1,2-结构单元的含量为85-95重量％，该液体聚丁二烯中1,4-结构单元的含量为5-15重量％，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1-2：1，所述液体聚丁二烯在45℃时的动力粘度为100-500P。
根据本发明的第二个方面，本发明提供了一种液体聚丁二烯的制备方法，该方法包括：在阴离子聚合反应条件下，将1,3-丁二烯与结构调节剂和有机锂引发剂在聚合溶剂中接触，得到含有聚丁二烯的聚合反应混合液，所述接触在-10℃至20℃的温度下进行，所述结构调节剂含有组分A和组分B，所述组分A为选自醚和胺中的一种或两种以上，所述组分B为选自碱金属醇盐中的一种或两种以上，有机锂引发剂：组分A：组分B的摩尔比为1：0.05-0.3：0.03-0.2，所述有机锂引发剂以锂计；
所述组分A为选自式I所示的化合物和式II所示的化合物中的一种或两种以上，
Figure PCTCN2020124445-appb-000001
式I中，R 1和R 2相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
R 3和R 4相同或不同，各自独立地为C 1-C 6的烷基，
n为1-5的整数；
Figure PCTCN2020124445-appb-000002
式II中，R 5和R 6相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
R 7和R 8相同或不同，各自独立地为C 1-C 6的亚烷基，R 9、R 10、R 11、R 12、R 13、R 14、R 15和R 16相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
m为1-5的整数。
根据本发明的第三个方面，本发明提供了由本发明第二个方面所述的方法制备的液体聚丁二烯。
根据本发明的第四个方面，本发明提供了一种组合物，该组合物含有液体聚丁二烯以及至少一种添加剂，所述液体聚丁二烯为本发明第一个方面或者第三个方面 所述的液体聚丁二烯。
根据本发明的第五个方面，本发明提供了一种聚合物涂层，该聚合物涂层含有本发明第一个方面或者第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明的第六个方面，本发明提供了一种胶粘剂，该胶粘剂含有本发明第一个方面或者第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明第七个方面，本发明提供了一种交联剂，该交联剂含有本发明第一个方面或者第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明的第八个方面，本发明提供了根据本发明第一个方面或者第三个方面所述的液体聚丁二烯、或者根据本发明第四个方面所述的组合物作为交联剂、胶粘剂或电绝缘材料的用途。
根据本发明的液体聚丁二烯，不仅具有较高的乙烯基含量，而且分子量分布窄，同时具有适宜的分子量和动力粘度。根据本发明的液体聚丁二烯具有良好的流动性能，成膜性和涂布性能好，特别适用于形成聚合物涂层，形成的聚合物涂层对基材具有提高的附着力。根据本发明的液体聚丁二烯在交联剂、粘合剂和电绝缘材料领域具有良好的应用前景。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，术语“液体聚丁二烯”是指在25℃的温度下具有流动性的聚丁二烯。
根据本发明的第一个方面，本发明提供了一种液体聚丁二烯，该液体聚丁二烯的数均分子量为2500-5500，分子量分布指数为1-1.2，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为85-95重量％，该液体聚丁二烯中1,4-结构单元的含量为5-15重量％，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1-2：1，所述液体聚丁二烯在45℃时的动力粘度为100-500P。
根据本发明的液体聚丁二烯，该液体聚丁二烯的数均分子量(M n)为2500-5500。 优选地，所述液体聚丁二烯的数均分子量为2800-5000。更优选地，所述液体聚丁二烯的数均分子量为3000-4500。
根据本发明的液体聚丁二烯，该液体聚丁二烯的分子量分布指数(M w/M n)为1-1.2。根据本发明的液体聚丁二烯，该液体聚丁二烯的分子量分布指数优选1.01-1.09，更优选为1.02-1.06。
本发明中，液体聚丁二烯的分子量和分子量分布指数采用凝胶渗透色谱分析测定，凝胶渗透色谱分析采用日本东曹公司的HLC-8320型凝胶渗透色谱仪，色谱柱为TSKgel SuperMultiporeHZ-N，标准柱为TSKgel SuperMultiporeHZ，溶剂为色谱纯四氢呋喃(THF)，以窄分布聚苯乙烯为标准样品，将聚合物样品配制成质量浓度为1mg/mL的四氢呋喃溶液，进样量为10.00μL，流速为0.35mL/min，测试温度为40.0℃。
根据本发明的液体聚丁二烯，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为85-95重量％。优选地，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为87重量％以上，例如可以为87-94重量％。更优选地，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为90重量％以上，优选为90-93重量％，例如90、90.1、90.2、90.3、90.4、90.5、90.6、90.7、90.8、90.9、91、91.1、91.2、91.3、91.4、91.5、91.6、91.7、91.8、91.9、92、92.1、92.2、92.3、92.4、92.5、92.6、92.7、92.8、92.9或者93重量％。
根据本发明的液体聚丁二烯，该液体聚丁二烯中1,4-结构单元的含量为5-15重量％。根据本发明的液体丁二烯，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1-2：1，优选为1.3-1.9：1。根据本发明的液体聚丁二烯，在一个优选的实例中，该液体聚丁二烯中反1,4-结构单元与顺1,4-结构单元的摩尔比为1.65-1.75：1。根据该优选实例的液体聚丁二烯形成的聚合物涂层对基材具有更高的附着力，显示出更高的剥离强度。
本发明中，术语“1,2-结构单元”是指丁二烯以1,2-聚合方式形成的结构单元，1,2-结构单元的含量也可以称为乙烯基含量；本发明中，术语“1,4-结构单元”是指丁二烯以1,4-聚合方式形成的结构单元。
本发明中，术语“顺1,4-结构单元”是指丁二烯以1,4-聚合方式形成且构型为顺式的结构单元，即下式所示的结构单元：
Figure PCTCN2020124445-appb-000003
本发明中，术语“反1,4-结构单元”是指丁二烯以1,4-聚合方式形成且构型为反式的结构单元，即下式所示的结构单元：
Figure PCTCN2020124445-appb-000004
本发明中，1,2-结构单元、1,4-结构单元、顺1,4-结构单元、以及反1,4-结构单元的含量均采用核磁共振波谱法测定，具体测试方法为：采用Bruker AVANCE400型超导核磁共振波仪测试， 1H核的共振频率为300.13MHz，谱宽为2747.253Hz，脉冲宽度为5.0μs，数据点为16K，样品管直径为5mm，溶剂为氘代氯仿(CDCl 3)，样品浓度为15mg/mL，测试温度为常温，扫描次数为16次，以四甲基硅烷化学位移为0ppm定标。
根据本发明的液体聚丁二烯，该液体聚丁二烯在45℃时的动力粘度为100-500泊(P)，具有良好的流动性，特别适合用于涂料和胶粘剂。优选地，根据本发明的液体聚丁二烯在45℃时的动力粘度为150-350P。更优选地，根据本发明的液体聚丁二烯在45℃时的动力粘度为170-300P。进一步优选地，根据本发明的液体聚丁二烯在45℃时的动力粘度为180-250P。
根据本发明的液体聚丁二烯动力粘度随分子量的变化不大，能在较宽的范围内显示出适宜的动力粘度。根据本发明的液体聚丁二烯，在一个优选的实例中，该液体聚丁二烯的数均分子量为2500-4000，优选为3000-4000，该液体聚丁二烯在45℃时的动力粘度为100-280P，优选为150-260P。在该优选的实例中，所述液体聚丁二烯的分子量分布指数可以为1-1.05。
根据本发明的液体聚丁二烯，在另一个优选的实例中，该液体聚丁二烯的数均分子量为大于4000且不大于5500，该液体聚丁二烯在45℃时的动力粘度为大于280P且不超过500P，优选为280-480P。在该优选的实例中，所述液体聚丁二烯的分子量分布指数可以为1-1.08。
本发明中，动力粘度参照GBT10247-2008中规定的毛细管法测定，其中，采用 尺寸号为4B的乌氏粘度计在45℃的温度下测定。
根据本发明的液体聚丁二烯，该液体聚丁二烯的玻璃化转变温度(T g)为-32℃至-12℃，优选为-29℃至-15℃，更优选为-27℃至-17℃。
本发明中，玻璃化转变温度采用差示扫描量热法测定，具体测试方法为：采用TA-2980DSC差示扫描量热仪按照“GB/T 29611-2013生橡胶，玻璃化转变温度”中规定的方法测定，升温速率为20℃/min。
根据本发明的液体聚丁二烯，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中金属元素的重量含量可以为200ppm以下，优选为100ppm以下，更优选为50ppm以下，进一步优选为20ppm以下。
本发明中，液体聚丁二烯中金属元素的含量采用等离子体法测定，具体测试方法为：采用美国珀金埃尔默(PE)公司Optima 8300型全谱直读ICP光谱仪，配备中阶梯光栅、固态检测器、紫外光区和可见光区双光路双固态检测器，采用平板等离子体技术；仪器操作参数如下：高频功率1300W，等离子气流量15L/min，雾化气流量0.55L/min，辅助气流量0.2L/min，蠕动泵速1.50mL/min，积分时间10s，等离子体轴向观测。样品制备方法如下：准确称取样品2.000g于瓷坩埚中，置于高温电阻炉内逐级升温至500℃，灰化完全后取出，加5mL 10体积％稀硝酸，在电热板上缓慢加热直至完全溶解，溶液蒸至尽干，加入1mL浓硝酸(浓度为68体积％)，转入50mL容量瓶中，并用水定容，同时制备试剂空白溶液。
根据本发明的第二个方面，本发明提供了一种液体聚丁二烯的制备方法，该方法包括：在阴离子聚合反应条件下，将1,3-丁二烯与结构调节剂和有机锂引发剂在聚合溶剂中接触，得到含有聚丁二烯的聚合反应混合液，所述接触在不高于40℃的温度下进行。
根据本发明的制备方法，所述结构调节剂含有组分A和组分B，所述组分A为选自醚和胺中的一种或两种以上，所述组分B为选自碱金属醇盐中的一种或两种以上。
根据本发明的制备方法，所述组分A为选自式I所示的化合物和式II所示的化合物中的一种或两种以上：
Figure PCTCN2020124445-appb-000005
式I中，R 1和R 2相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
R 3和R 4相同或不同，各自独立地为C 1-C 6的烷基，
n为1-5的整数，例如可以为：1、2、3、4或5；
Figure PCTCN2020124445-appb-000006
式II中，R 5和R 6相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
R 7和R 8相同或不同，各自独立地为C 1-C 6的亚烷基，R 9、R 10、R 11、R 12、R 13、R 14、R 15和R 16相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
m为1-5的整数，例如可以为：1、2、3、4或5。
式I和式II中，C 1-C 6的烷基包括C 1-C 6的直链烷基和C 3-C 6的支链烷基，其具体实例可以包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基和正己基。
在一种优选的实施方式中，式I中，R 1和R 2均为氢原子；R 3和R 4相同，为甲基、乙基、正丙基或正丁基。
在一种优选的实施方式中，式II中，R 5和R 6均为氢原子，R 7和R 8为C 2-C 4的亚烷基，R 9、R 10、R 11、R 12、R 13、R 14、R 15和R 16均为氢原子。
根据本发明的制备方法，所述组分A的优选实例可以包括但不限于：二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二正丙醚、二乙二醇二正丁醚和1,2-二哌啶基乙烷中的一种或两种以上。
所述碱金属醇盐优选为选自式III所示的化合物中的一种或两种以上，
R 17-O-M  (式III)
式III中，R 17为C 1-C 20的烷基、C 6-C 30的芳基或者C 4-C 20的环烷基，优选为C 2-C 10 的烷基或者C 6-C 12的环烷基，更优选为C 2-C 6的烷基；
M为碱金属原子，例如可以为Li、Na或者K，优选为Na。
式III中，C 1-C 20的烷基包括C 1-C 20的直链烷基和C 3-C 20的支链烷基，其具体实例可以包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基及其异构体、正己基及其异构体、正庚基及其异构体、正辛基及其异构体、正壬基及其异构体、正癸基及其异构体、十一烷基及其异构体、十二烷基及其异构体、十三烷基及其异构体、十四烷基及其异构体、十五烷基及其异构体、十六烷基及其异构体、十七烷基及其异构体、十八烷基及其异构体、十九烷基及其异构体和二十烷基及其异构体。
式III中，C 4-C 20的环烷基包括环丙基、环戊基、环己基、4-甲基环己基、4-乙基环己基、4-正丙基环己基、4-正丁基环己基或者2-异丙基-5-甲基环己基。
根据本发明的制备方法，所述碱金属醇盐的优选实例可以包括但不限于：叔丁氧基钠、叔戊氧基钠、薄荷醇钠、乙氧基钠和正己醇钠中的一种或两种以上。
根据本发明的制备方法，有机锂引发剂：组分A：组分B的摩尔比为1：0.05-0.3：0.03-0.2，所述有机锂引发剂以锂计。优选地，有机锂引发剂：组分A：组分B的摩尔比为1：0.08-0.25：0.04-0.18，所述有机锂引发剂以锂计。更优选地，有机锂引发剂：组分A：组分B的摩尔比为1：0.1-0.2：0.05-0.15，所述有机锂引发剂以锂计。根据本发明的制备方法，组分B：组分A的摩尔比优选为0.4-1.5：1，更优选为0.5-1：1。
根据本发明的制备方法，所述有机锂引发剂优选为有机单锂化合物，更优选为式IV所示的化合物，
R 18Li     (式IV)
式IV中，R 18为C 1-C 6的烷基、C 3-C 12的环烷基、C 7-C 14的芳烷基或者C 6-C 12的芳基。
式IV中，C 1-C 6的烷基包括C 1-C 6的直链烷基和C 3-C 6的支链烷基，其具体实例可以包括但不限于：甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、叔戊基、新戊基和正己基。
式IV中，C 3-C 12的环烷基的具体实例可以包括但不限于：环丙基、环戊基、环己基、4-甲基环己基、4-乙基环己基、4-正丙基环己基和4-正丁基环己基。
式IV中，C 7-C 14的芳烷基的具体实例可以包括但不限于：苯基甲基、苯基乙基、 苯基正丙基、苯基正丁基、苯基叔丁基、苯基异丙基、苯基正戊基和苯基正丁基。
式IV中，C 6-C 12的芳基的具体实例可以包括但不限于：苯基、萘基、4-甲基苯基和4-乙基苯基。
根据本发明的制备方法，所述有机锂引发剂的具体实例可以包括但不限于：乙基锂、正丙基锂、异丙基锂、正丁基锂、仲丁基锂、叔丁基锂、苯基锂、2-萘基锂、4-丁基苯基锂、4-甲苯基锂、环己基锂和4-丁基环己基锂中的一种或两种以上。优选地，所述有机锂引发剂为正丁基锂和/或仲丁基锂，更优选地，所述有机锂引发剂为正丁基锂。
所述有机锂引发剂的用量可以根据预期的液体聚丁二烯的分子量进行选择。优选地，所述有机锂引发剂的用量使得制备的液体聚丁二烯的数均分子量为2500-5500，优选为2800-5000，更优选为3000-4500。根据预期的聚合物分子量大小确定有机锂引发剂的具体用量的方法是本领域技术人员熟知的，本文不再详述。
根据本发明的制备方法，所述聚合溶剂可以为各种能够作为反应媒介并使聚合反应在溶液聚合条件下进行的有机物质，例如可以为烃类溶剂。所述聚合溶剂可以为选自环己烷、正己烷、正戊烷、正庚烷、苯和抽余油中的一种或两种以上。所述抽余油是在石油炼制过程中，富含芳烃的催化重整产物经萃取芳烃后剩余的馏分油。所述聚合溶剂可以单独使用，也可以混合使用。
根据本发明的制备方法，以聚合溶剂和1,3-丁二烯的总量为基准，1,3-丁二烯的含量(即，单体含量)可以为1-15重量％，优选为2-12重量％，更优选为4-10重量％。本发明中，单体含量是指进行聚合反应之前，以聚合溶剂和1,3-丁二烯的总量为基准确定的1,3-丁二烯的重量百分含量。
根据本发明的制备方法，将1,3-丁二烯与结构调节剂和有机锂引发剂在-10℃至20℃的温度下于聚合溶剂中接触，从而进行阴离子聚合反应，例如：将1,3-丁二烯与结构调节剂和有机锂引发剂在-10℃、-9℃、-8℃、-7℃、-6℃、-5℃、-4℃、-3℃、-2℃、-1℃、0℃、1℃、2℃、3℃、4℃、5℃、6℃、7℃、8℃、9℃、10℃、11℃、12℃、13℃、14℃、15℃、16℃、17℃、18℃、19℃或者20℃的温度下进行接触。更优选地，将1,3-丁二烯与结构调节剂和有机锂引发剂在不高于10℃的温度下进行接触，如-5℃至10℃的温度下进行接触。
根据本发明的制备方法，阴离子聚合反应可以在0.005-1.5MPa的压力下进行，更优选在0.1-1MPa的压力下进行。本发明中，所述压力均指表压。根据本发明的制 备方法，阴离子聚合反应的时间可以根据聚合反应的温度进行选择，一般可以为30-240min，优选为40-120min。
根据本发明的制备方法，阴离子聚合反应在由非活性气体形成的气氛中进行。所述非活性气体是指在聚合条件下与反应物、反应生成物以及溶剂均不发生化学相互作用的气体，例如：氮气和/或第零族元素气体(如氩气)。
根据本发明的制备方法，该制备方法还可以包括：脱除所述聚合反应混合液中的至少部分金属离子，得到纯化聚合反应混合液。可以将所述聚合反应混合液进行洗涤，从而脱除至少部分金属离子。
在一种优选的实施方式中，脱除所述聚合反应混合物中的至少部分金属离子的方法包括：将所述聚合反应混合液与洗涤液混合，从混合物中分离出油相，所述洗涤液为水或者含有酸的水溶液。在该优选的实施方式中，所述酸优选为无机酸，更优选为硫酸、硝酸、盐酸和碳酸中的一种或两种以上。在所述酸为碳酸时，可以通过向聚合反应混合液与水的混合物中通入二氧化碳气体和/或向聚合反应混合液中添加干冰，从而形成碳酸。
在该优选的实施方式的一个更为优选的实例中，所述洗涤液包括第一洗涤液和第二洗涤液，所述第一洗涤液为含有酸I的水溶液，所述第二水溶液为含有酸II的水溶液，所述酸I为硫酸、盐酸和硝酸中的一种或两种以上，所述酸II为碳酸，脱除所述聚合反应混合液中的至少部分金属离子的方法包括：将聚合反应混合物液与第一洗涤液混合，得到第一混合物，从第一混合物中分离出第一油相，脱除所述第一油相中的至少部分聚合溶剂，得到液体聚丁二烯粗产品；在二氧化碳的存在将所述第一油相与水混合，得到第二混合物，从第二混合物中分离出第二油相，脱除所述第二油相中的至少部分挥发性组分，得到液体聚丁二烯。在该更为优选的实例中，所述第一洗涤液与1,3-丁二烯的重量比优选为0.5-5：1，更优选为2-4：1，所述第一洗涤液中的酸I与有机锂引发剂的摩尔比优选为0.1-1.5：1，更优选为0.2-1：1，进一步优选为0.3-0.6：1，所述酸I以H +计；所述第二洗涤液与1,3-丁二烯的重量比为1-2：1。所述第二洗涤液中的酸II与有机锂引发剂的摩尔比为优选为0.1-1.5：1，更优选为0.2-1：1，进一步优选为0.3-0.6：1，所述酸I以H +计。
根据本发明的第三个方面，本发明提供了一种由本发明第二个方面所述的方法制备的液体聚丁二烯。
采用本发明第二个方面所述的方法制备的液体聚丁二烯，不仅具有高的乙烯基 含量，而且分子量分布窄，同时具有适宜的分子量和动力粘度。根据本发明的液体聚丁二烯具有良好的流动性能，成膜性和涂布性能好，特别是以含有本发明的液体聚丁二烯的涂料形成的涂层，对基材具有提高的附着力。
根据本发明的第四个方面，本发明提供了一种组合物，该组合物含有液体聚丁二烯以及至少一种添加剂，其中，所述液体聚丁二烯为本发明第一个方面所述的液体聚丁二烯。
所述添加剂可以为能赋予组合物新性能和/或改善组合物已有性能的物质。作为一个优选的实例，所述添加剂含有抗氧剂。所述抗氧剂可以为常规选择，例如，所述抗氧剂可以为酚类和/或胺类抗氧剂。具体地，所述抗氧剂可以为4,6-二辛基硫代甲基邻甲酚、四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(即，抗氧剂264)、亚磷酸三(2,4-二叔丁基苯基)酯(即，抗氧剂168)、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯(即，抗氧剂1076)、2,6-二叔丁基对甲酚、叔丁基邻苯二酚和2,2’-亚甲基-双(4-甲基-6-叔丁基苯酚)中的一种或两种以上。相对于100重量份的液体聚丁二烯，所述抗氧剂的含量可以为0.005-2重量份，优选为0.01-1重量份。
根据本发明的第五个方面，本发明提供了一种聚合物涂层，该聚合物涂层含有本发明第一个方面或第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明的聚合物涂层对基材具有较高的附着力。
根据本发明的第六个方面，本发明提供了一种胶粘剂，该胶粘剂含有本发明第一个方面或第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明的第七个方面，本发明提供了一种交联剂，该交联剂含有本发明第一个方面或第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物。
根据本发明的第八个方面，本发明提供了本发明第一个方面或第三个方面所述的液体聚丁二烯、或者本发明第四个方面所述的组合物作为交联剂、胶粘剂或者电绝缘材料的应用。
以下将结合实施例对本发明进行详细描述，但并不因此限制本发明的范围。
在没有特别说明的情况下，常温和室温均表示25±3℃。
以下实施例和对比例中，液体聚丁二烯的1,2-结构单元含量采用Bruker AVANCE400型超导核磁共振波仪测定， 1H核的共振频率为300.13MHz，谱宽为2747.253Hz，脉冲宽度为5.0μs，数据点为16K，样品管直径为5mm，溶剂为氘代氯 仿(CDCl 3)，样品浓度为15mg/mL，测试温度为常温，扫描次数为16次，以四甲基硅烷化学位移为0ppm定标。
以下实施例和对比例中，液体聚丁二烯的分子量和分子量分布指数采用凝胶渗透色谱分析测定，凝胶渗透色谱分析采用日本东曹公司的HLC-8320型凝胶渗透色谱仪，色谱柱为TSKgel SuperMultiporeHZ-N，标准柱为TSKgel SuperMultiporeHZ，溶剂为色谱纯四氢呋喃(THF)，以窄分布聚苯乙烯为标准样品，将聚合物样品配制成质量浓度为1mg/mL的四氢呋喃溶液，进样量为10.00μL，流速为0.35mL/min，测试温度为40.0℃。
以下实施例和对比例中，液体聚丁二烯的玻璃化转变温度采用TA-2980DSC差示扫描量热仪按照GB/T 29611-2013生橡胶，玻璃化转变温度中规定的方法测定，升温速率为20℃/min。
以下实施例和对比例中，液体聚丁二烯中金属元素的含量采用等离子体法测定，具体测试方法为：采用美国珀金埃尔默(PE)公司Optima 8300型全谱直读ICP光谱仪，配备中阶梯光栅、固态检测器、紫外光区和可见光区双光路双固态检测器，采用平板等离子体技术；仪器操作参数如下：高频功率1300W，等离子气流量15L/min，雾化气流量0.55L/min，辅助气流量0.2L/min，蠕动泵速1.50mL/min，积分时间10s，等离子体轴向观测。样品制备方法如下：准确称取样品2.000g于瓷坩埚中，置于高温电阻炉内逐级升温至500℃，灰化完全后取出，加5mL 10％(V％)稀硝酸，在电热板上缓慢加热直至完全溶解，溶液蒸至尽干，加入1mL浓硝酸(浓度为68体积％)，转入50mL容量瓶中，并用水定容，同时制备试剂空白溶液。
以下实施例和对比例中，液体聚丁二烯在45℃时的动力粘度参照GBT10247-2008中规定的毛细管法测定，其中，采用尺寸号为4B的乌氏粘度计在45℃的温度下测定。
以下实施例和对比例中，涉及以下化学试剂：
抗氧剂264、抗氧剂168和抗氧剂1076购自国药试剂公司；
环己烷：购自国药试剂公司，纯度＞99.9％，分子量筛浸泡15天，水含量低于5ppm(重量含量)；
1,3-丁二烯：聚合级，购自燕山石化；
正丁基锂：购自百灵威试剂公司，为1.6mol/L的己烷溶液；
二乙二醇二甲醚(2G，分子量134)：购自百灵威试剂公司，分析纯；
二乙二醇二乙醚：购自百灵威试剂公司，分析纯；
二乙二醇二丁醚：购自百灵威试剂公司，分析纯；
1,2-二哌啶基乙烷(DPE，分子量196)：购自百灵威试剂公司，分析纯；
叔戊氧基钠(STA，分子量110)：购自百灵威试剂公司，1.4mol/L的四氢呋喃溶液；
薄荷醇钠(SMT，分子量178)：伊诺凯试剂公司提供，1.0mol/L四氢呋喃溶液；
乙氧基钠(SEO，分子量68)：购自百灵威试剂公司，纯度96％，配制成0.2mol/L的四氢呋喃溶液；
N,N,N’,N’-四甲基乙二胺(TMEDA)：购自百灵威试剂公司，分析纯；
甲基吗啉：购自国药试剂有限公司，分析纯；
硫酸：购自百灵威试剂公司，浓度为98重量％，用水配制成20重量％溶液；
硝酸：购自国药试剂公司，浓度为68重量％，用水配制成20重量％溶液。
实施例1
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
(1)在氮气保护下，向5L反应器中加入环己烷、结构调节剂1、结构调节剂2、1,3-丁二烯(种类和用量见表1所示，表中所列用量均以纯化合物计量)，控制反应器温度为10℃以下，向5L反应器中加入设计量的正丁基锂(用量见表1所示，表中所列用量均以纯化合物计量)；并在表1列出的温度和反应压力下进行阴离子聚合反应，得到含有聚丁二烯的聚合反应混合液。
(2)向步骤(1)得到的聚合反应混合液中添加水和酸(具体用量和酸的种类在表2中列出，表中所列用量均以纯化合物计量)，搅拌15分钟后，进行静置分层，分离出水相，将得到的油相进行减压蒸馏，脱除液体聚丁二烯粗品。
(3)向步骤(2)得到的液体聚丁二烯粗品中添加水，伴随搅拌通入二氧化碳气体(水和二氧化碳的具体用量在表2中列出)，然后静置分层，分离出水相，将得到的油相进行减压蒸馏，向蒸馏残余物中添加抗氧剂(具体用量和种类在表2中列出)，得到含有根据本发明的液体聚丁二烯的组合物PB1。制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例2-7
实施例2-7用于说明本发明的液体聚丁二烯及其制备方法。
实施例2-7采用与实施例1相同的方法制备液体聚丁二烯，不同的是，在表1列出的条件下制备含有根据本发明的液体聚丁二烯的组合物PB2-PB7，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例8
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，正丁基锂加入量为50mmol，得到含有根据本发明的液体聚丁二烯的组合物PB8，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例9
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(2)中水的用量为200g，得到含有根据本发明的液体聚丁二烯的组合物PB9，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例10
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(2)中硫酸的用量为30mmol，得到含有根据本发明的液体聚丁二烯的组合物PB10，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例11
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，不进行步骤(3)，得到含有根据本发明的液体聚丁二烯的组合物PB11，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例12
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(2)中所用的酸为硝酸，以H +计算，硝酸的摩尔用量与实施例1中的硫酸的摩尔用量相同，得到含有根据本发明的液体聚丁二烯的组合物PB12，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例13
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中结构调节剂1为二乙二醇二乙醚，得到含有根据本发明的液体聚丁二烯的组合物PB13，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
实施例14
本实施例用于说明本发明的液体聚丁二烯及其制备方法。
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中结构调节剂1为二乙二醇二丁醚，得到含有根据本发明的液体聚丁二烯的组合物PB14，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例1
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中结构调节剂1二乙二醇二甲醚的用量为0.4g，得到含有液体聚丁二烯的组合物DPB1，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例2
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中不采用结构调节剂2叔戊氧基钠，而是只采用结构调节剂1二乙二醇二甲醚，得到含有液体聚丁二烯的组合物DPB2，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例3
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，聚合反应的温度为50℃，得到含有液体聚丁二烯的组合物DPB3，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例4
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，聚合反应的温度为50℃，并且不采用结构调节剂2叔戊氧基钠，而是只采用结构调节剂1二乙二醇二甲醚，得到含有液体聚丁二烯的组合物DPB4，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例5
采用与实施例1相同的方法制备聚丁二烯，不同的是，步骤(1)中，正丁基锂用量为3mmol，得到含有聚丁二烯的组合物DPB5，其中，制备的聚丁二烯的结构性质参数在表3中列出。
对比例6
采用与实施例1相同的方法制备聚丁二烯，不同的是，步骤(1)中，正丁基锂用量为3mmol，二乙二醇二甲醚为0.08g，叔戊氧基钠为0.3mmol，得到含有聚丁二烯的组合物DPB6，其中，制备的聚丁二烯的结构性质参数在表3中列出。
对比例7
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，溶剂为四氢呋喃，用量为2300g，引发剂为萘钠，用量为70mmol，不加入二乙二醇二甲醚和叔戊氧基钠，得到含有聚丁二烯的组合物DPB7，其中，制备的聚丁二烯的结构性质参数在表3中列出。
对比例8
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，用等量的TMEDA代替二乙二醇二甲醚，用等量的SMT代替STA，得到含有液体聚丁二 烯的组合物DPB8，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例9
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，用TMEDA代替二乙二醇二甲醚，不加入STA，得到含有液体聚丁二烯的组合物DPB9，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例10
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，用等量的TMEDA代替二乙二醇二甲醚，得到含有液体聚丁二烯的组合物DPB10，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例11
采用与实施例1相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，正丁基锂的用量为125mmol，得到含有液体聚丁二烯的组合物DPB11，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
对比例12
在1L烧瓶中装入338g正己烷，冷却至-40℃。向其中添加25ml的仲丁基锂的环己烷溶液(1.0mol·L -1)，然后滴加84g在-78℃液化的丁二烯，然后向聚合液中添加18g的THF，在-20℃搅拌4小时，得到液体聚丁二烯DPB12，其中，制备的液体聚丁二烯的结构性质在表3中列出。
对比例13
在1L烧瓶中装入338g正己烷，冷却至-40℃。向其中添加85ml的仲丁基锂的环己烷溶液(1.0mol·L -1)，然后滴加84g在-78℃液化的丁二烯，然后向聚合液中添加18g的THF，在-20℃搅拌120分钟，得到液体聚丁二烯DPB13，其中，制备的液体聚丁二烯的结构性质在表3中列出。
对比例14
在1L烧瓶中装入338g正己烷，冷却至-40℃。向其中添加56ml的仲丁基锂的环己烷溶液(1.0mol·L -1)，然后滴加84g在-78℃液化的丁二烯，然后向聚合液中添加18g的THF，在-20℃搅拌120分钟，得到聚丁二烯DPB14，其中，制备的液体聚丁二烯的结构性质在表3中列出。
对比例15
采用与实施例7相同的方法制备液体聚丁二烯，不同的是，步骤(1)中，1,2-二哌啶基乙烷用等量的甲基吗啉代替，得到含有液体聚丁二烯的组合物DPB15，其中，制备的液体聚丁二烯的结构性质参数在表3中列出。
表1
Figure PCTCN2020124445-appb-000007
表1(续表)
实施例 1 8 13 14
聚合溶剂种类 环己烷 环己烷 环己烷 环己烷
聚合溶剂用量/g 2300 2300 2300 2300
1,3-丁二烯用量/g 250 250 250 250
正丁基锂用量/mmol 70 50 70 70
结构调节剂1种类 2G 2G 二乙二醇二乙醚 二乙二醇二丁醚
结构调节剂1用量/g 1.2 1.2 1.2 1.2
结构调节剂2种类 STA STA STA STA
结构调节剂2用量/mmol 7 7 7 7
聚合反应温度 0℃ 0℃ 0℃ 0℃
聚合反应压力 0.3MPa 0.3MPa 0.3MPa 0.3MPa
聚合反应时间 90min 90min 90min 90min
表2
Figure PCTCN2020124445-appb-000008
表3
Figure PCTCN2020124445-appb-000009
Figure PCTCN2020124445-appb-000010
1：以聚丁二烯的总量为基准，1,2-结构单元的含量
2：以聚丁二烯的总量为基准，顺1,4-结构单元的含量
3：以聚丁二烯的总量为基准，反1,4-结构单元的含量
4和 5：日本曹达液体聚丁二烯产品
测试例
采用实施例1至实施例14制备得到的组合物，将其均匀涂布于铜箔表面，涂层厚度为0.6mm，在120℃交联固化2小时，采用IPC-TM-650 2.4.08C中规定的方法测定剥离强度，实验结果在表4中列出。
测试对比例
采用与测试例相同的方法对对比例1-4和7-15制备的组合物以及B3000和B2000的剥离强度进行测定，实验结果在表4中列出。
表4
样品编号 剥离强度(N/mm)
PB1 0.92
PB2 0.90
PB3 0.93
PB4 0.90
PB5 0.86
PB6 0.86
PB7 0.85
PB8 0.88
PB9 0.91
PB10 0.90
PB11 0.91
PB12 0.92
PB13 0.88
PB14 0.85
DPB1 0.71
DPB2 0.82
DPB3 0.81
DPB4 0.68
DPB7 0.83
DPB8 0.81
DPB9 0.76
DPB10 0.73
DPB11 0.78
DPB12 0.82
DPB13 0.57
DPB14 0.64
DPB15 0.71
B3000 0.84
B2000 0.79
从表3和4可以看出，根据本发明的液体聚丁二烯不仅具有高的1,2-结构单元含量，窄的分子量分布，并且分子量以及在45℃时的动力粘度适中，具有良好的流动性能，涂布性能和成膜性能好，交联固化后形成的聚合物涂层对基材的附着能力强。其中，对比例11、13和14制备的液体聚丁二烯的动力粘度小，涂布性能和成膜性能较差，难以形成厚度均匀且性能均一的聚合物涂层。
另外，根据本发明的液体聚丁二烯的金属离子含量低。根据本发明的液体聚丁二烯适合作为交联剂、胶粘剂或电绝缘材料。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (25)

  1. 一种液体聚丁二烯，该液体聚丁二烯的数均分子量为2500-5500，分子量分布指数为1-1.2，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为85-95重量％，该液体聚丁二烯中1,4-结构单元的含量为5-15重量％，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1-2：1，所述液体聚丁二烯在45℃时的动力粘度为100-500P。
  2. 根据权利要求1所述的液体聚丁二烯，其中，该液体聚丁二烯中顺1,4-结构单元与反1,4-结构单元的摩尔比为1.3-1.9：1，优选为1.65-1.75：1。
  3. 根据权利要求1或2所述的液体聚丁二烯，其中，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中1,2-结构单元的含量为87-94重量％，优选为90-93重量％。
  4. 根据权利要求1所述的液体聚丁二烯，其中，该液体聚丁二烯的数均分子量为2800-5000，优选为3000-4500。
  5. 根据权利要求1或4所述的液体聚丁二烯，其中，该液体聚丁二烯的分子量分布指数为1.01-1.09，优选为1.02-1.06。
  6. 根据权利要求1-5中任意一项所述的液体聚丁二烯，其中，以该液体聚丁二烯的总量为基准，该液体聚丁二烯中金属元素的重量含量为200ppm以下，优选为100ppm以下，更优选为50ppm以下，进一步优选为20ppm以下。
  7. 根据权利要求1-6中任意一项所述的液体聚丁二烯，其中，该液体聚丁二烯的玻璃化转变温度为-32℃至-12℃，优选为-27℃至-17℃。
  8. 根据权利要求1-7中任意一项所述的液体聚丁二烯，其中，该液体聚丁二烯在45℃时的动力粘度为150-350P，优选为170-300P，更优选为180-250P。
  9. 根据权利要求1-3、6和7中任意一项所述的液体聚丁二烯，其中，该液体 聚丁二烯的数均分子量为2500-4000，优选为3000-4000，该液体聚丁二烯在45℃时的动力粘度为100-280P，优选为150-260P；
    优选地，该液体聚丁二烯的分子量分布指数为1-1.05。
  10. 根据权利要求1-3、6和7中任意一项所述的液体聚丁二烯，其中，该液体聚丁二烯的数均分子量为大于4000且不大于5500，该液体聚丁二烯在45℃时的动力粘度为大于280P且不超过500P，优选为280-480P；
    优选地，该液体聚丁二烯的分子量分布指数为1-1.08。
  11. 一种液体聚丁二烯的制备方法，该方法包括：在阴离子聚合反应条件下，将1,3-丁二烯与结构调节剂和有机锂引发剂在聚合溶剂中接触，得到含有聚丁二烯的聚合反应混合液，所述接触在-10℃至20℃的温度下进行，所述结构调节剂含有组分A和组分B，所述组分A为选自醚和胺中的一种或两种以上，所述组分B为选自碱金属醇盐中的一种或两种以上，有机锂引发剂：组分A：组分B的摩尔比为1：0.05-0.3：0.03-0.2，所述有机锂引发剂以锂计；
    所述组分A为选自式I所示的化合物和式II所示的化合物中的一种或两种以上，
    Figure PCTCN2020124445-appb-100001
    式I中，R 1和R 2相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
    R 3和R 4相同或不同，各自独立地为C 1-C 6的烷基，
    n为1-5的整数；
    Figure PCTCN2020124445-appb-100002
    式II中，R 5和R 6相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
    R 7和R 8相同或不同，各自独立地为C 1-C 6的亚烷基，R 9、R 10、R 11、R 12、R 13、 R 14、R 15和R 16相同或不同，各自独立地为氢原子或者C 1-C 6的烷基，
    m为1-5的整数。
  12. 根据权利要求11所述的方法，其中，所述组分A为选自二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二正丙醚、二乙二醇二正丁醚和1,2-二哌啶基乙烷中的一种或两种以上。
  13. 根据权利要求11或12所述的方法，其中，所述碱金属醇盐为选自式III所示的化合物中的一种或两种以上，
    R 17-O-M  (式III)
    式III中，R 17为C 1-C 20的烷基、C 6-C 30的芳基或者C 4-C 20的环烷基，
    M为碱金属原子；
    优选地，所述组分B为选自叔丁氧基钠、叔戊氧基钠、薄荷醇钠、乙氧基钠和正己醇钠中的一种或两种以上。
  14. 根据权利要求11-13中任意一项所述的方法，其中，有机锂引发剂：组分A：组分B的摩尔比为1：0.1-0.2：0.05-0.15，所述有机锂引发剂以锂计。
  15. 根据权利要求11-14中任意一项所述的方法，其中，组分B：组分A的摩尔比为0.4-1.5：1，优选为0.5-1：1。
  16. 根据权利要求11-15中任意一项所述的方法，其中，所述有机锂引发剂的用量使得制备得到的液体丁二烯的数均分子量为2500-5500，优选为2800-5000，更优选为3000-4500；
    优选地，所述有机锂引发剂为选自式IV所示的化合物中的一种或两种以上，
    R 18Li  (式IV)
    式IV中，R 18为C 1-C 6的烷基、C 3-C 12的环烷基、C 7-C 14的芳烷基或者C 6-C 12的芳基；
    更优选地，所述有机锂引发剂为正丁基锂和/或仲丁基锂。
  17. 根据权利要求11-16中任意一项所述的方法，其中，所述接触在-5℃至10℃的温度下进行。
  18. 根据权利要求11-17中任意一项所述的方法，其中，以聚合溶剂和1,3-丁二烯的总量为基准，所述1,3-丁二烯的含量为1-15重量％，优选为4-10重量％。
  19. 一种由权利要求11-18中任意一项所述的方法制备的液体聚丁二烯。
  20. 一种组合物，该组合物含有液体聚丁二烯以及至少一种添加剂，所述液体聚丁二烯为权利要求1-10和19中任意一项所述的液体聚丁二烯。
  21. 根据权利要求20所述的组合物，其中，所述添加剂含有抗氧剂。
  22. 一种聚合物涂层，该聚合物涂层含有权利要求1-10和19中任意一项所述的液体聚丁二烯聚合物、或者权利要求20和21中任意一项所述的组合物。
  23. 一种胶粘剂，该胶粘剂含有权利要求1-10和19中任意一项所述的液体聚丁二烯、或者权利要求20和21中任意一项所述的组合物。
  24. 一种交联剂，该交联剂含有权利要求1-10和19中任意一项所述的液体聚丁二烯、或者权利要求20和21中任意一项所述的组合物。
  25. 权利要求1-10和19中任意一项所述的液体聚丁二烯、或者权利要求20和21中任意一项所述的组合物作为交联剂、胶粘剂或电绝缘材料的用途。
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