WO2017157330A1 - 苯乙烯衍生物的功能性聚合物及其阴离子聚合制备方法 - Google Patents

苯乙烯衍生物的功能性聚合物及其阴离子聚合制备方法 Download PDF

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WO2017157330A1
WO2017157330A1 PCT/CN2017/077071 CN2017077071W WO2017157330A1 WO 2017157330 A1 WO2017157330 A1 WO 2017157330A1 CN 2017077071 W CN2017077071 W CN 2017077071W WO 2017157330 A1 WO2017157330 A1 WO 2017157330A1
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group
monomer
polymer
styrene
aryl
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French (fr)
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韩丙勇
陈健
鲁建民
黄明路
张爱民
陈大魁
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浙江众立合成材料科技股份有限公司
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Priority to JP2018548793A priority Critical patent/JP7025343B2/ja
Priority to EP17765872.1A priority patent/EP3431518A4/en
Priority to US16/086,064 priority patent/US10927208B2/en
Publication of WO2017157330A1 publication Critical patent/WO2017157330A1/zh

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    • 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
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/10—Copolymers 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 with vinyl-aromatic monomers
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C08F12/28—Amines
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/06—Butadiene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/08—Isoprene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

  • the invention relates to the field of polymers and preparation techniques thereof, and in particular to a functional polymer of a styrene derivative and an anionic polymerization preparation method thereof.
  • a functional polymer refers to a type of polymer obtained by introducing a functional reactive group or a hetero atom into a polymer chain and modifying the polymer, which greatly expands the application range of the material, so that It plays an important role in promoting polymer blending, improving compatibility with inorganic fillers, and preparing new polymers with different structures.
  • the functionalization of end group functionalized polymers is primarily by functional modification of the polymer ends with initiators and blocking agents containing functional reactive groups or heteroatoms.
  • the functionalized styrene is copolymerized with a general monomer such as styrene or butadiene to obtain a chain.
  • a functionalized functional polymer mainly introduce hetero atom-containing groups in the side groups of the polymer chain, thereby realizing functionalization and high performance of the polymer.
  • functional monomers have defects such as complicated synthetic routes and high costs, which restrict the application in practice. Therefore, it is a significant subject to develop low-cost functional monomers, prepare low-cost functional polymers, and achieve various functional functions of polymers.
  • the anionic polymerization method is the most classical living polymerization method, which can precisely control the molecular weight and structure of the polymer.
  • the design of synthetic structures with novel and complex structures by anionic living polymerization has become a research hotspot in the field of polymer polymerization.
  • the existing anionic polymerization method has the following drawbacks: (1) Only a small number of monomers can achieve anionic polymerization, and many polymers containing functional groups cannot be prepared by anionic polymerization, which limits the development of polymer varieties. (2) Anionic polymerization has high selectivity to comonomers, and monomers with relatively large difference in activity cannot substantially achieve random copolymerization. Therefore, it is necessary to develop a functional monomer suitable for anionic polymerization to expand the range of the anionic polymerization monomer; and at the same time, the monomer is copolymerized with a conventional anionic polymerization monomer to realize the functionalization of the conventional anionic polymerization product.
  • the styrene derivative of the present invention can be random or block copolymerized with a conventional monomer such as styrene, a conjugated diene or the like, and the obtained functional polymer can be easily further chemically modified;
  • the amount of the styrene derivative added can easily adjust the basic properties of the functional polymer, such as glass transition temperature, viscoelasticity and the like.
  • a first aspect of the invention provides a functional polymer of a styrene derivative which is a copolymer of monomer A having a structure of formula (I) and other comonomers:
  • R 1 and R 2 are the same or different and are independently selected from H, C 1-6 alkyl, C 1-6 alkoxy;
  • R 3 is selected from -CR 4 R 5 R 6 , -OR 7 , -SR 8 or -SnR 9 ;
  • R 4 is selected from H, C 1-6 alkyl, aryl or heteroaryl, and the alkyl, aryl, heteroaryl group may be substituted by a substituent such as a C 1-6 alkyl group. , C 1-6 alkoxy, aryl, etc.;
  • R 5 and R 6 are the same or different, and R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from an aryl group or a heteroaryl group, and the aryl group or heteroaryl group may be substituted with a substituent.
  • the substituent is, for example, a C 1-6 alkyl group, a C 1-6 alkoxy group, an aryl group or the like.
  • the alkyl group means a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl. , tert-butyl, sec-butyl, pentyl, neopentyl.
  • the aryl group means a monocyclic or polycyclic aromatic group having 6 to 20 (preferably 6 to 14) carbon atoms, and representative aryl groups include phenyl, naphthyl, anthracenyl, ⁇ .
  • the heteroaryl group means a monocyclic or polycyclic heteroaromatic group having 1 to 20 carbon atoms and 1 to 4 hetero atoms selected from N, S, O, and a representative heteroaryl group. Including: thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, thiazolyl, indolyl, azaphthyl, azaindol, azaindolyl and the like.
  • the other comonomer is any monomer which can be copolymerized with the vinyl group in the monomer A by an anionic polymerization method.
  • the other comonomer is selected from one or more of styrene, alpha-methyl styrene or conjugated dienes.
  • the conjugated diene is, for example, butadiene, 1,3-pentadiene, isoprene or the like.
  • the molar percentage (M A ) of the monomer A is: 0 ⁇ M A ⁇ 100 mol%
  • the molar percentage (M B ) of the other comonomer is: 0 ⁇ M B ⁇ 100 mol%.
  • 0 ⁇ M A ⁇ 50 mol% more preferably 0 ⁇ M A ⁇ 20 mol%, still more preferably, 0 ⁇ M A ⁇ 15 mol%.
  • the polymer has a number average molecular weight Mn of from 300 to 300,000, preferably from 3,000 to 260,000, more preferably from 4,000 to 25,000; a molecular weight distribution MWD of from 1.05 to 2.00, using a gel permeation chromatograph ( GPC) determination.
  • Mn number average molecular weight of from 300 to 300,000, preferably from 3,000 to 260,000, more preferably from 4,000 to 25,000; a molecular weight distribution MWD of from 1.05 to 2.00, using a gel permeation chromatograph ( GPC) determination.
  • GPC gel permeation chromatograph
  • R 1 and R 2 are the same and are selected from H or C 1-6 alkyl.
  • R 3 is selected from -CR 4 R 5 R 6 .
  • R 4 is selected from H or C 1-6 alkyl;
  • R 5 and R 6 are the same or different and are independently selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
  • the substituent is, for example, a C 1-6 alkyl group, a C 1-6 alkoxy group, an aryl group or the like.
  • the aryl group is, for example, a phenyl group or a naphthyl group;
  • the heteroaryl group is, for example, a pyridine.
  • R 1 the present invention is the same as R 2, is selected from H, methyl or ethyl;
  • R 3 is selected from -CR 4 R 5 R 6;
  • R 4 is selected from H, methyl Or an ethyl group;
  • R 5 and R 6 are the same or different and are selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridine, for example, C 1-6 Alkyl, C 1-6 alkoxy, aryl, and the like.
  • a second aspect of the present invention provides a method for preparing a functional polymer of the above styrene derivative, which comprises preparing a copolymer of the monomer A and another comonomer by a solution polymerization method using butyllithium as an initiator. .
  • the butyllithium is, for example, n-butyllithium, sec-butyllithium or tert-butyllithium. More preferably, the butyllithium is n-butyllithium.
  • the specific steps of the process are as follows: monomer A and other comonomers are added to a system containing butyllithium, an activator and a solvent, and the copolymer is prepared by a solution polymerization process.
  • the solvent is, for example, cyclohexane or a mixture of cyclohexane and hexane (volume ratio of 7:3 to 9:1).
  • the activator is, for example, tetrahydrofuran (THF) or other oxygen- or nitrogen-containing but active hydrogen-free compound such as tetrahydrofurfuryl ethyl ether, N,N-dimethyltetrahydrofurfurylamine or the like.
  • the monomer concentration is 5-20% by weight; the molar ratio of butyl lithium to monomer is 1: (50-3000); activator (such as THF, The molar ratio of tetrahydrofurfuryl ethyl ether or N,N-dimethyltetrahydrofurfurylamine to butyllithium is (0.2-40):1.
  • the polymerization temperature is from 25 to 100 ° C; the polymerization time is from 20 min to 720 min.
  • the solvent is removed by the end of the polymerization to obtain the copolymer.
  • the invention provides a brand new functional polymer, firstly expanding the living anion polymerizable monomer, and the polymer has a complex topology, and the functional side groups introduced in the polymer are easily further chemically modified. Sex is a promising functional polymer.
  • the present invention provides a monomer which is particularly suitable for living anionic polymerization (i.e., monomer A having the structure represented by formula (I)), which monomer has low selectivity to comonomer, various properties and structures.
  • the comonomer can be copolymerized with it by an anionic method to prepare a series of copolymers of the monomer A and other comonomers (ie, the functional polymer of the present invention); in addition, by adjusting the amount of the monomer added, Adjustments to the basic properties of the functional polymer, such as glass transition temperature, viscoelastic properties, and the like, can be readily achieved.
  • the monomer A of the present invention is a kind of good living anionic polymerization monomer, and can be copolymerized with other active anionic polymerization monomers by an anionic polymerization method to obtain a kind of performance. And functional polymers with a wide range of applications.
  • the present invention provides a functional polymer of a styrene derivative which is a copolymer of the monomer A having a structure represented by the formula (I) and other comonomers. It has been found through research that the functional polymer can be easily further chemically modified in addition to being particularly suitable for preparation by an anionic polymerization method; at the same time, it can be easily adjusted by adjusting the amount of the styrene derivative added. Adjustments to the basic properties of the functional polymer, such as glass transition temperature, etc., are achieved. Specifically, the above object can be well achieved by controlling the molar percentage of the monomer A in the polymer.
  • 0 ⁇ M A ⁇ 50 mol% preferably 0 ⁇ M A ⁇ 20 mol%, still more preferably, 0 ⁇ M A ⁇ 15 mol%. It has been found that when the M A is low, the general polymer modification can be realized; when the M A is high, the polymer will have new properties, such as a large change in the glass transition temperature, viscoelastic energy, and the like of the polymer.
  • the present invention also provides a method for preparing a functional polymer of the above styrene derivative, in particular, the method comprises preparing a monomer A and other by a solution polymerization method using butyllithium as an initiator. a copolymer of comonomers.
  • the monomer concentration is 5-20 wt%; the molar ratio of butyl lithium to monomer is 1/50-1/3000; an activator (such as THF, tetrahydrofurfuryl ethyl ether or N, N)
  • an activator such as THF, tetrahydrofurfuryl ethyl ether or N, N
  • the molar ratio of -dimethyltetrahydrofurfurylamine to butyllithium is (0.2-40):1.
  • the polymerization temperature is 25-100 ° C; the polymerization time is 20 min to 720 min; the solvent is removed at the end of the polymerization to obtain the copolymer.
  • butyl lithium (such as n-butyllithium, sec-butyllithium or tert-butyllithium, preferably n-butyllithium) which is commonly used in anionic polymerization is used as an initiator; commonly used tetrahydrofuran (THF), tetrahydrofurfuryl alcohol An ether or N,N-dimethyltetrahydrofurfurylamine as an activator; in the choice of solvent, the present invention uses cyclohexane, which is commonly used in anionic solution polymerization, as a solvent, or a mixture of cyclohexane and hexane ( The volume ratio is from 7:3 to 9:1); it can be seen that the present invention achieves anionic polymerization of the monomer A with other comonomers by simple conditions.
  • a stepwise charging method is employed as in the conventional method of preparing a block copolymer. Specifically, the following steps are taken:
  • a quantity of solvent and activator are added to the reaction apparatus to maintain the system temperature at 25-100 ° C (e.g., 30-70 ° C, specifically 50 ° C) while maintaining agitation.
  • the metered monomer A and the initiator butyl lithium are then added for a reaction, and the reaction is carried out for 10-30 minutes before entering the second stage reaction.
  • the metered monomer A is added to the reaction system to carry out a three-stage reaction, and the reaction is terminated after 10-30 minutes, and the solvent is removed to obtain the block copolymer.
  • the solvent is cyclohexane or a mixture of cyclohexane and hexane (volume ratio of 7:3 to 9:1);
  • the activator is Tetrahydrofuran (THF), tetrahydrofurfuryl ethyl ether or N,N-dimethyltetrahydrofurfurylamine;
  • the butyl lithium is, for example, n-butyllithium, sec-butyllithium or tert-butyllithium, preferably n-butyl lithium.
  • DPES p-(2,2-diphenylethyl)styrene
  • the polymer had a number average molecular weight of 4,800 and a molecular weight distribution of 1.06. It is indicated that the anionic polymerization of the monomer enables molecular weight design synthesis and a narrow molecular weight distribution.
  • the glass transition temperature of the polymer was 89 °C.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPES-butadiene random copolymer in which the molar percentage of DPES was 7.56 mol%.
  • test data of the DPES-butadiene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPES-styrene random copolymer in which the molar percentage of DPES was 13.53 mol%.
  • test data of the DPES-styrene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPES-isoprene random copolymer in which the molar percentage of DPES was 9.28 mol%.
  • test data of the DPES-isoprene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPES-styrene-butadiene ternary random copolymer, wherein the molar percentage of DPES was 4.52 mol%. .
  • test data of the DPES-styrene-butadiene ternary random copolymer is shown in Table 1.
  • DPAMS p-(N,N-diphenylaminomethyl)styrene
  • test data of the DPAMS homopolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPAMS-butadiene random copolymer in which the molar percentage of DPAMS was 10.86 mol%.
  • test data of the DPAMS-butadiene random copolymer are shown in Table 1.
  • test data of the DPAMS-styrene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPAMS-isoprene random copolymer in which the molar percentage of DPAMS was 9.28 mol%.
  • test data of the DPAMS-isoprene random copolymer are shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DPAMS-styrene-butadiene ternary random copolymer, wherein the molar percentage of DPAMS was 2.30 mol%. .
  • test data of the DPAMS-styrene-butadiene ternary random copolymer is shown in Table 1.
  • DMAPES p-(2,2-bis(4-dimethylaminophenyl)ethyl)styrene
  • test data of the DMAPES homopolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DMAPES-butadiene random copolymer in which the molar percentage of DMAPES was 8.58 mol%.
  • test data of the DMAPES-butadiene random copolymer is shown in Table 1.
  • test data of the DMAPES-styrene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DMAPES-isoprene random copolymer in which the molar percentage of DMAPES was 7.30 mol%.
  • test data of the DMAPES-isoprene random copolymer is shown in Table 1.
  • the reaction was terminated with ethanol, and the polymer was precipitated with a large amount of ethanol, and dried in a vacuum oven to obtain a DMAPES-styrene-butadiene ternary random copolymer, wherein the molar percentage of DMAPES was 1.78 mol%. .
  • test data of the DMAPES-styrene-butadiene ternary random copolymer is shown in Table 1.
  • PBOMS p-(phenoxymethyl)styrene
  • Example Number average molecular weight The molecular weight distribution Example Number average molecular weight The molecular weight distribution 1 4800 1.06 11 5500 1.05 2 36000 1.10 12 213700 1.20 3 113100 1.18 13 112600 1.23 4 231100 1.18 14 38000 1.15 5 4900 1.09 15 4800 1.05 6 5300 1.09 16 5100 1.05 7 245000 1.20 17 22000 1.09 8 102000 1.18 18 99000 1.11 9 34500 1.15 19 35900 1.11 10 5100 105 20 5100 123
  • Example 2 The DPES-butadiene random copolymer in Example 2 is exemplified, and the glass transition temperature of the DPES-butadiene random copolymer is changed as shown in Table 2 by adjusting the amount of the DPES added.

Abstract

一种苯乙烯衍生物的功能性聚合物及其制备方法，所述聚合物为具有式（I）所示结构的单体A和其他共聚单体的共聚物。所述苯乙烯衍生物的功能性聚合物可以很容易地实现进一步地化学改性；同时，通过调整所述苯乙烯衍生物的加入量，可以很容易地实现所述功能性聚合物的基本性能的调整，如玻璃化温度、粘弹性能等。

Description

苯乙烯衍生物的功能性聚合物及其阴离子聚合制备方法 技术领域
本发明涉及聚合物及其制备技术领域，尤其是涉及一种苯乙烯衍生物的功能性聚合物及其阴离子聚合制备方法。
背景技术
功能性聚合物是指将具有功能性的反应基团或者杂原子引入聚合物链中，对聚合物进行改性而得到的一类聚合物，这极大扩大了材料的应用范围，使其在促进聚合物共混、改善与无机填料相容性、制备不同结构新型聚合物等方面发挥重要作用。目前，端基官能化聚合物的功能化主要是通过用含有功能性的反应基团或者杂原子的引发剂和封端剂进行聚合物末端的功能性改性。
近年来，许多研究人员开发带有功能性的反应基团或者杂原子的聚合单体，通过其与通用单体的共聚，从而提供一种链中官能化的功能性聚合物的制备方法。这种方法可以调控官能团的种类、数量和位置，从而能够精确地合成结构可控的功能性聚合物。例如有文献报道利用1,1-二(4-二甲胺基苯基)乙烯[Lingling Wu,Yanshai Wang,Yurong Wang.In-chain multi-functionalized polystyrene by living anionic copolymerization with1,1-bis(4-dimethylaminophenyl)ethylene:Synthesis and effect on the dispersity of carbon black in polymer-based composites.Polymer 2013；54,2958-2965]或叔胺基苯乙烯(如N-异丙基-N-三甲基硅-4-乙烯基苄胺、N,N-二甲基-4-乙烯基苯胺、N,N-二甲基-4-乙烯基苄胺或N,N-二甲基-4-乙烯基苯乙胺等)[Kazunori Se,Anionic living polymerization of useful monomers that can provide intermolecular chemical links.Prog.Polym.Sci.2003；28,583-618]等官能化苯乙烯与苯乙烯、丁二烯等通用单体共聚得到链中官能化的功能性聚合物。这类功能性聚合物主要是在聚合物链的侧基引入含杂原子的基团，从而实现聚合物的功能化和高性能化。一般而言，功能性单体存在合成路线复杂、成本高等缺陷，制约在实际中的应用。因此开发低成本功能性单体、制备低成本功能性聚合物、实现聚合物的多种功能性作用是一个有意义的课题。
阴离子聚合方法是最经典的活性聚合方法，能够对聚合物分子量以及结构进行精确的控制。目前通过阴离子活性聚合的方法设计合成结构新颖，具有功能性的复杂聚合物已经成为高分子聚合领域的研究热点。
但是，现有的阴离子聚合方法存在如下缺陷：(1)只有少数的单体能够实现阴离子聚合，很多含有官能团的聚合物不能通过阴离子聚合反应制备得到，限制了聚合物品种的发展。(2)阴离子聚合对共聚单体的选择性要求高，活性差别比较大的单体基本不能实现无规共聚。因此，有必要开发适合于阴离子聚合的功能性单体，以拓展阴离子聚合单体范围；同时该单体与传统阴离子聚合单体进行共聚，可实现传统阴离子聚合产品的功能化。
发明内容
本发明的目的在于提供一种新型的苯乙烯衍生物的功能性聚合物及其阴离子聚合制备方法。本发明的苯乙烯衍生物能够和传统单体如苯乙烯、共轭二烯烃等实现无规或嵌段共聚，所得的功能性聚合物可以很容易地实现进一步化学改性；同时，通过调整所述苯乙烯衍生物的加入量，可以很容易地实现所述功能性聚合物的基本性能的调整，如玻璃化温度、粘弹性能等。
本发明的第一方面是提供一种苯乙烯衍生物的功能性聚合物，所述聚合物为具有式(I)所示结构的单体A和其他共聚单体的共聚物：
Figure PCTCN2017077071-appb-000001
式(I)中，
R1、R2相同或不同，彼此独立地选自H、C1-6烷基、C1-6烷氧基；
R3选自-CR4R5R6、-OR7、-SR8或-SnR9；
R4选自H、C1-6烷基、芳基或杂芳基，所述烷基、芳基、杂芳基可以被取代基取代，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等；
R5和R6相同或不同，R5、R6、R7、R8、R9彼此独立地选自芳基或杂芳基，所述芳基、杂芳基可以被取代基取代，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。
根据本发明，所述烷基指具有1-6个碳原子的直连或支链烷基，所述烷基例如为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基。
根据本发明，所述芳基指具有6-20个(优选6-14个)碳原子的单环或多环芳族基团，代表性的芳基包括：苯基、萘基、蒽基、芘基等。
根据本发明，所述的杂芳基指具有1-20个碳原子、1-4个选自N、S、O杂原子的单环或多环杂芳族基团，代表性的杂芳基包括：噻吩基、呋喃基、吡咯基、吡啶基、嘧啶基、咪唑基、噻唑基、吲哚基、氮杂萘基、氮杂蒽基、氮杂芘基等。
根据本发明，所述的其他共聚单体为任何可以与单体A中的乙烯基通过阴离子聚合方法实现共聚的单体。不限定地，所述其他共聚单体选自苯乙烯、α-甲基苯乙烯或共轭二烯烃中的一种或多种。所述共轭二烯烃例如为丁二烯、1,3-戊二烯、异戊二烯等。
根据本发明，所述单体A的摩尔百分含量(MA)为：0<MA<100mol％，所述其他共聚单体的摩尔百分含量(MB)为：0<MB<100mol％。优选地，0<MA≤50mol％，更优选地，0<MA≤20mol％，还更优选地，0<MA≤15mol％。
根据本发明，所述聚合物的数均分子量Mn为300-300000，优选地，为3000-260000，更优选地，为4000-255000；分子量分布MWD为1.05-2.00，用凝胶渗透色谱仪(GPC)测定。
根据本发明，式(I)中，优选地，R1、R2相同，选自H或C1-6烷基。优选地，R3选自-CR4R5R6。优选地，R4选自H或C1-6烷基；R5和R6相同或不同，彼此独立地选自取代或未取代的芳基、或取代或未取代的杂芳基，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。所述芳基例如为苯基、萘基；所述杂芳基例如为吡啶。
根据本发明，式(I)中，优选地，R1、R2相同，选自H、甲基或乙基；R3选自-CR4R5R6；R4选自H、甲基或乙基；R5、R6相同或不同，选自取代或未取代的苯基、取代或未取代的萘基、或取代或未取代的吡啶，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。
本发明的第二方面是提供一种上述苯乙烯衍生物的功能性聚合物的制备方法，以丁基锂为引发剂，采用溶液聚合方法制备所述单体A与其他共聚单体的共聚物。
根据本发明，所述丁基锂例如为正丁基锂、仲丁基锂或叔丁基锂。更优选地，所述丁基锂为正丁基锂。
根据本发明，所述方法的具体步骤如下：将单体A和其他共聚单体加入含有丁基锂、活化剂和溶剂的体系中，采用溶液聚合方法制备所述共聚物。
根据本发明，所述溶剂例如为环己烷或环己烷与己烷混合物(体积比7：3到9：1)。所 述活化剂例如为四氢呋喃(THF)或其它含氧或含氮的但不含活性氢的化合物，如四氢糠醇乙基醚、N,N-二甲基四氢糠胺等。
根据本发明，加入单体A和其他共聚单体的体系中，单体浓度为5-20wt％；丁基锂与单体的摩尔比为1:(50-3000)；活化剂(如THF、四氢糠醇乙基醚或N,N-二甲基四氢糠胺)与丁基锂的摩尔比为(0.2-40):1。
根据本发明，聚合温度为25-100℃；聚合时间为20min到720min。聚合结束脱除溶剂得到所述共聚物。
根据本发明，若制备嵌段共聚物，则采用分步加料的方式。
本发明的有益效果：
本发明提供了一种全新的功能性聚合物，首先拓展了可活性阴离子聚合的单体，而且所述聚合物具有复杂拓扑结构，聚合物中引入的功能性侧基很容易进行进一步地化学改性，是一种极具开发前景的功能性聚合物。
本发明提供了一种特别适合于活性阴离子聚合的单体(即具有式(I)所示结构的单体A)，该单体对共聚单体的选择性不高，多种性能和结构的共聚单体均能够与其通过阴离子方法共聚，制备了一系列所述单体A与其他共聚单体的共聚物(即本发明的功能性聚合物)；另外，通过调整该单体的加入量，可以很容易地实现所述功能性聚合物的基本性能的调整，如玻璃化温度、粘弹性能等。
具体实施方式
20世纪80年代日本学者Otsu研究发现许多含苯基的多取代乙烷型化合物在光照或者受热条件下，可以产生活性低或者结构稳定的自由基。对于此类化合物，如果结构不对称，则可以生成两种活性不同的自由基。例如含有1,1,2-三苯乙烷化合物在加热的情况下能够产生两种不同的自由基，其中活性较高的自由基可以做为引发剂引发单体进行自由基聚合。中国专利(申请号：201110285596.0)报道了一类端基含有这种结构的大分子引发剂，其在加热的情况下可逆热分解产生自由基，并能够引发自由基聚合。但关于这类化合物用于功能性聚合物的制备的还鲜有报道。我们通过研究发现，本发明的单体A，是一类很好的可活性阴离子聚合的单体，通过阴离子聚合方法，可以将其与其他可活性阴离子聚合的单体共聚，制得一类性能和应用前景很广泛的功能性聚合物。
如上所述，本发明提供一种苯乙烯衍生物的功能性聚合物，所述聚合物为具有式(I)所示结构的单体A和其他共聚单体的共聚物。通过研究发现，所述功能性聚合物除了特别适合 于阴离子聚合方法制备以外，还可以很容易地实现进一步地化学改性；同时，通过调整所述苯乙烯衍生物的加入量，可以很容易地实现所述功能性聚合物的基本性能的调整，如玻璃化温度等。具体而言，通过控制所述单体A在聚合物中的摩尔百分含量，可以很好的实现上述目的。例如，优选地，0<MA≤50mol％，更优选地，0<MA≤20mol％，还更优选地，0<MA≤15mol％。研究发现，MA较低时，可实现通用聚合物改性；MA较高时，聚合物将能够具有新的性能，如较大幅度改变聚合物的玻璃化温度，粘弹性能等。
如上所述，本发明还提供了制备上述苯乙烯衍生物的功能性聚合物的方法，具体而言，所述方法以丁基锂为引发剂，采用溶液聚合方法制备所述单体A与其他共聚单体的共聚物。
以无规共聚物为例，以环己烷或环己烷与己烷混合物(体积比7：3到9：1)为溶剂、四氢呋喃(THF)、四氢糠醇乙基醚或N,N-二甲基四氢糠胺为活化剂、丁基锂为引发剂，将单体A和其他共聚单体加入含有上述溶剂、活化剂和引发剂的体系中，采用溶液聚合方法制备所述共聚物。其中，所述体系中，单体浓度为5-20wt％；丁基锂与单体的摩尔比为1/50-1/3000；活化剂(如THF、四氢糠醇乙基醚或N,N-二甲基四氢糠胺)与丁基锂的摩尔比为(0.2-40):1。聚合过程中，聚合温度为25-100℃；聚合时间为20min到720min；聚合结束脱除溶剂得到所述共聚物。
本发明中，采用阴离子聚合常用的丁基锂(如正丁基锂、仲丁基锂或叔丁基锂，优选正丁基锂)作为引发剂；常用的四氢呋喃(THF)、四氢糠醇乙基醚或N,N-二甲基四氢糠胺作为活化剂；在溶剂的选择上，本发明采用阴离子溶液聚合普遍使用的环己烷为溶剂，或者采用环己烷与己烷的混合物(体积比7：3到9：1)；可见，本发明通过简单的条件实现了所述单体A与其他共聚单体的阴离子聚合。
以嵌段共聚物为例，除了采用上述的溶剂、活化剂和引发剂之外，与常规的嵌段共聚物的制备方法一样，采用分步加料方式。具体而言，采用以下步骤：
首先，将一定量的溶剂以及活化剂加入反应装置，在保持搅拌的同时，使体系温度保持在25-100℃(例如30-70℃，具体如50℃)。然后加入计量的所述单体A和引发剂丁基锂进行一段反应，反应进行10-30min后进入二段反应。
将计量的其他共聚单体(如苯乙烯、α-甲基苯乙烯或共轭二烯烃中的一种或者多种)加入反应体系，进行二段反应，反应进行20-80min后进入三段反应。
将计量的所述单体A加入反应体系，进行三段反应，反应10-30min后终止反应，脱除溶剂后得到所述嵌段共聚物。
同上，所述溶剂为环己烷或环己烷与己烷混合物(体积比7：3到9：1)；所述活化剂为 四氢呋喃(THF)、四氢糠醇乙基醚或N,N-二甲基四氢糠胺；所述丁基锂例如为正丁基锂、仲丁基锂或叔丁基锂，优选正丁基锂。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同方面的应用，在没有背离本发明的精神下进行各种修饰或改变。
实施例1(对-(2,2-二苯基乙基)苯乙烯均聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入1g对-(2,2-二苯基乙基)苯乙烯(DPES)单体(设计分子量为5000)，再依次加入0.5ml四氢呋喃、0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱干燥后得到DPES均聚物。该聚合物数均分子量4800，分子量分布为1.06。说明该单体的阴离子聚合能够进行分子量设计合成，且分子量分布窄。聚合物的玻璃化温度为89℃。
所述均聚物的测试数据见表1。
实施例2(DPES-丁二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3gDPES单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，加入0.0096mmol的N,N-二甲基四氢糠胺，加入0.0192ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPES-丁二烯无规共聚物，其中，DPES的摩尔百分含量为7.56mol％。
所述DPES-丁二烯无规共聚物的测试数据见表1。
实施例3(DPES-苯乙烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.45gDPES单体，依次加入10ml环己烷、1.05g苯乙烯(St)、0.0039mmol的N,N-二甲基四氢糠胺和0.0077ml的正丁基锂溶液(浓度1.3mmol/mL)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPES-苯乙烯无规共聚物，其中，DPES的摩尔百分含量为13.53mol％。
所述DPES-苯乙烯无规共聚物的测试数据见表1。
实施例4(DPES-异戊二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.45gDPES单体，依 次加入10ml环己烷、1.05g异戊二烯(Ip)、0.0016mmol的N,N-二甲基四氢糠胺和0.0031ml的正丁基锂溶液(浓度1.3mmol/ml)，50℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPES-异戊二烯无规共聚物，其中，DPES的摩尔百分含量为9.28mol％。
所述DPES-异戊二烯无规共聚物的测试数据见表1。
实施例5(DPES-苯乙烯-丁二烯三元无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.2gDPES单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，依次加入0.2g苯乙烯、0.077mmol的N,N-二甲基四氢糠胺和0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPES-苯乙烯-丁二烯三元无规共聚物，其中，DPES的摩尔百分含量为4.52mol％。
所述DPES-苯乙烯-丁二烯三元无规共聚物的测试数据见表1。
实施例6(对-(N,N-二苯基胺基甲基)苯乙烯均聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入1g对-(N,N-二苯基胺基甲基)苯乙烯(DPAMS)单体(设计分子量为5000)，依次加入0.5ml四氢呋喃、10ml环己烷和0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱干燥后得到DPAMS均聚物。
所述DPAMS均聚物的测试数据见表1。
实施例7(DPAMS-丁二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.45gDPAMS单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，加入0.0016ml的N,N-二甲基四氢糠胺，加入0.0031ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPAMS-丁二烯无规共聚物，其中，DPAMS的摩尔百分含量为10.86mol％。
所述DPAMS-丁二烯无规共聚物的测试数据见表1。
实施例8(DPAMS-苯乙烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3g DPAMS单体，依次加入10ml环己烷、0.7g苯乙烯和0.0039mmol的N,N-二甲基四氢糠胺，加入0.0077ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPAMS-苯乙烯无规共聚物，其中，DPAMS的 摩尔百分含量为13.53mol％。
所述DPAMS-苯乙烯无规共聚物的测试数据见表1。
实施例9(DPAMS-异戊二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3g DPAMS单体，依次加入10ml环己烷、0.7g异戊二烯和0.011mmol的N,N-二甲基四氢糠胺，加入0.022ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPAMS-异戊二烯无规共聚物，其中，DPAMS的摩尔百分含量为9.28mol％。
所述DPAMS-异戊二烯无规共聚物的测试数据见表1。
实施例10(DPAMS-苯乙烯-丁二烯三元无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.1g DPAMS单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，依次加入0.2g苯乙烯和0.077mmol的N,N-二甲基四氢糠胺，加入0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DPAMS-苯乙烯-丁二烯三元无规共聚物，其中，DPAMS的摩尔百分含量为2.30mol％。
所述DPAMS-苯乙烯-丁二烯三元无规共聚物的测试数据见表1。
实施例11(对-(2,2-二(4-二甲基胺基苯基)乙基)苯乙烯均聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入1g对-(2,2-二(4-二甲基胺基苯基)乙基)苯乙烯(DMAPES)单体(设计分子量为5000)，依次加入0.5ml四氢呋喃与10ml环己烷，加入0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱干燥后得到DMAPES均聚物。
所述DMAPES均聚物的测试数据见表1。
实施例12(DMAPES-丁二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.45g DMAPES单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，加入0.0019mmol的N,N-二甲基四氢糠胺，加入0.0038ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DMAPES-丁二烯无规共聚物，其中，DMAPES的摩尔百分含量为8.58mol％。
所述DMAPES-丁二烯无规共聚物的测试数据见表1。
实施例13(DMAPES-苯乙烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3g DMAPES单体，依次加入10ml环己烷、0.7g苯乙烯和0.0039mmol的N,N-二甲基四氢糠胺，加入0.0077ml的正丁基锂(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DMAPES-苯乙烯无规共聚物，其中，DMAPES的摩尔百分含量为10.75mol％。
所述DMAPES-苯乙烯无规共聚物的测试数据见表1。
实施例14(DMAPES-异戊二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3g DMAPES单体，依次加入10ml环己烷、0.7g异戊二烯和0.0096mmol的N,N-二甲基四氢糠胺，加入0.0192ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DMAPES-异戊二烯无规共聚物，其中，DMAPES的摩尔百分含量为7.30mol％。
所述DMAPES-异戊二烯无规共聚物的测试数据见表1。
实施例15(DMAPES-苯乙烯-丁二烯三元无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.1g DMAPES单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，依次加入0.2g苯乙烯和0.077mmol的N,N-二甲基四氢糠胺，加入0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到DMAPES-苯乙烯-丁二烯三元无规共聚物，其中，DMAPES的摩尔百分含量为1.78mol％。
所述DMAPES-苯乙烯-丁二烯三元无规共聚物的测试数据见表1。
实施例16(对-(苯氧基甲基)苯乙烯均聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入1g对-(苯氧基甲基)苯乙烯(PBOMS)单体(设计分子量为5000)，依次加入0.5ml四氢呋喃、10ml环己烷和0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱干燥后得到PBOMS均聚物。
所述PBOMS均聚物的测试数据见表1。
实施例17(PBOMS-丁二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.45g对-(苯氧基甲基)苯乙烯(PBOMS)单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，加入0.0193mmol的N,N-二甲基四氢糠胺，加入0.0385ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到PBOMS-丁二烯无规共聚物，其中，PBOMS的摩尔百分含量为14.42mol％。
所述PBOMS-丁二烯无规共聚物的测试数据见表1。
实施例18(PBOMS-苯乙烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3gPBOMS单体，依次加入10ml环己烷、0.7g苯乙烯和0.0039mmol的N,N-二甲基四氢糠胺，加入0.0077ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到PBOMS-苯乙烯无规共聚物，其中，PBOMS的摩尔百分含量为17.78mol％。
所述PBOMS-苯乙烯无规共聚物的测试数据见表1。
实施例19(PBOMS-异戊二烯无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.3gPBOMS单体，依次加入10ml环己烷、0.7g异戊二烯和0.0096mmol的N,N-二甲基四氢糠胺，加入0.0192的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到PBOMS-异戊二烯无规共聚物，其中，PBOMS的摩尔百分含量为12.39mol％。
所述PBOMS-异戊二烯无规共聚物的测试数据见表1。
实施例20(PBOMS-苯乙烯-丁二烯三元无规共聚物的制备)
取一干净的聚合瓶，用火焰烘烤后抽真空然后充入氮气保护，加入0.1gPBOMS单体，用移液管移入10ml的丁二烯(Bd)的环己烷溶液(浓度为7g Bd/100ml环己烷)，依次加入0.2g苯乙烯和0.077mmol的N,N-二甲基四氢糠胺，加入0.154ml的正丁基锂溶液(浓度1.3mmol/ml)，40℃下反应6h。聚合结束后用乙醇终止反应，再用大量乙醇沉淀出聚合物，真空烘箱中烘干得到PBOMS-苯乙烯-丁二烯三元无规共聚物，其中，PBOMS的摩尔百分含量为3.16mol％。
所述PBOMS-苯乙烯-丁二烯三元无规共聚物的测试数据见表1。
表1实施例1-20的测试数据
实施例 数均分子量 分子量分布 实施例 数均分子量 分子量分布
1 4800 1.06 11 5500 1.05
2 36000 1.10 12 213700 1.20
3 113100 1.18 13 112600 1.23
4 231100 1.18 14 38000 1.15
5 4900 1.09 15 4800 1.05
6 5300 1.09 16 5100 1.05
7 245000 1.20 17 22000 1.09
8 102000 1.18 18 99000 1.11
9 34500 1.15 19 35900 1.11
10 5100 105 20 5100 123
实施例21
实施例2中的DPES-丁二烯无规共聚物为例，通过调整所述DPES的加入量，所述DPES-丁二烯无规共聚物的玻璃化温度的变化如表2所示。
表2
序号 DPES的摩尔百分比 玻璃化温度(Tg)(℃)
1 0.5 -55
2 1 -52
3 2 -50
4 3 -45
5 8 -30

Claims (9)

  1. 一种苯乙烯衍生物的功能性聚合物，其特征在于，所述聚合物为具有式(I)所示结构的单体A和其他共聚单体的共聚物：
    Figure PCTCN2017077071-appb-100001
    式(I)中，
    R1、R2相同或不同，彼此独立地选自H、C1-6烷基、C1-6烷氧基；
    R3选自-CR4R5R6、-OR7、-SR8或-SnR9；
    R4选自H、C1-6烷基、芳基或杂芳基，所述烷基、芳基、杂芳基可以被取代基取代，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等；
    R5和R6相同或不同，R5、R6、R7、R8、R9彼此独立地选自芳基或杂芳基，所述芳基、杂芳基可以被取代基取代，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。
  2. 根据权利要求1所述的苯乙烯衍生物的功能性聚合物，其特征在于，所述烷基指具有1-6个碳原子的直连或支链烷基，所述烷基例如为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基；
    所述芳基指具有6-20个(优选6-14个)碳原子的单环或多环芳族基团，代表性的芳基包括：苯基、萘基、蒽基、芘基等；
    所述的杂芳基指具有1-20个碳原子、1-4个选自N、S、O杂原子的单环或多环杂芳族基团，代表性的杂芳基包括：噻吩基、呋喃基、吡咯基、吡啶基、嘧啶基、咪唑基、噻唑基、吲哚基、氮杂萘基、氮杂蒽基、氮杂芘基等。
  3. 根据权利要求1或2所述的苯乙烯衍生物的功能性聚合物，其特征在于，所述的其他共聚单体为任何可以与单体A中的乙烯基通过阴离子聚合方法实现共聚的单体。
    优选地，所述其他共聚单体选自苯乙烯、α-甲基苯乙烯或共轭二烯烃中的一种或多种。优选地，所述共轭二烯烃例如为丁二烯、1,3-戊二烯、异戊二烯等。
  4. 根据权利要求1-3任一项所述的苯乙烯衍生物的功能性聚合物，其特征在于，所述单 体A的摩尔百分含量(MA)为：0<MA<100mol％，所述其他共聚单体的摩尔百分含量(MB)为：0<MB<100mol％。优选地，0<MA≤50mol％，更优选地，0<MA≤20mol％，还更优选地，0<MA≤15mol％。
    优选地，所述聚合物的数均分子量Mn为300-300000，优选地，为3000-260000，更优选地，为4000-255000；分子量分布MWD为1.05-2.00；用凝胶渗透色谱仪(GPC)测定。
  5. 根据权利要求1-4任一项所述的苯乙烯衍生物的功能性聚合物，其特征在于，式(I)中，R1、R2相同，选自H或C1-6烷基。优选地，R3选自-CR4R5R6。优选地，R4选自H或C1-6烷基；R5和R6相同或不同，彼此独立地选自取代或未取代的芳基、或取代或未取代的杂芳基，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。所述芳基例如为苯基、萘基；所述杂芳基例如为吡啶。
    优选地，式(I)中，R1、R2相同，选自H、甲基或乙基；R3选自-CR4R5R6；R4选自H、甲基或乙基；R5、R6相同或不同，选自取代或未取代的苯基、取代或未取代的萘基、或取代或未取代的吡啶，所述取代基例如为：C1-6烷基、C1-6烷氧基、芳基等。
  6. 权利要求1-5任一项所述的苯乙烯衍生物的功能性聚合物的制备方法，其特征在于，以丁基锂为引发剂，采用溶液聚合方法制备所述单体A与其他共聚单体的共聚物。
    优选地，所述丁基锂例如为正丁基锂、仲丁基锂或叔丁基锂。更优选地，所述丁基锂为正丁基锂。
  7. 根据权利要求6所述的制备方法，其特征在于，所述方法包括以下步骤：将单体A和其他共聚单体加入含有丁基锂、活化剂和溶剂的体系中，采用溶液聚合方法制备所述共聚物。
    优选地，所述溶剂例如为环己烷或环己烷与己烷混合物(体积比7：3到9：1)。优选地，所述活化剂例如为四氢呋喃(THF)或其它含氧或含氮的但不含活性氢的化合物，如四氢糠醇乙基醚、N,N-二甲基四氢糠胺等。
  8. 根据权利要求7所述的制备方法，其特征在于，加入单体A和其他共聚单体的体系中，单体浓度为5-20wt％；丁基锂与单体的摩尔比为1:(50-3000)；活化剂(如THF、四氢糠醇乙基醚或N,N-二甲基四氢糠胺)与丁基锂的摩尔比为(0.2-40):1。
    优选地，聚合温度为25-100℃；聚合时间为20min到720min。
    还更优选地，聚合结束脱除溶剂得到所述共聚物。
  9. 根据权利要求6-8任一项所述的制备方法，其特征在于，采用分步加料的方式制备嵌段共聚物。
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