WO2019024633A1 - 带可逆交联键的苯乙烯类共聚物及其制备方法 - Google Patents

带可逆交联键的苯乙烯类共聚物及其制备方法 Download PDF

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WO2019024633A1
WO2019024633A1 PCT/CN2018/093648 CN2018093648W WO2019024633A1 WO 2019024633 A1 WO2019024633 A1 WO 2019024633A1 CN 2018093648 W CN2018093648 W CN 2018093648W WO 2019024633 A1 WO2019024633 A1 WO 2019024633A1
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copolymer
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styrene
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styrene copolymer
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French (fr)
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张爱民
徐雨
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四川大学
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Priority claimed from CN201710652437.7A external-priority patent/CN107337772B/zh
Priority claimed from CN201710652415.0A external-priority patent/CN107337748B/zh
Priority claimed from CN201710652990.0A external-priority patent/CN107245134B/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
    • 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
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers

Definitions

  • the invention belongs to a styrenic copolymer, in particular to a styrene copolymer with a reversible crosslink and a preparation method thereof.
  • Styrene copolymers are a class of polymeric materials in which polystyrene segments are present in the molecular chain, such as polystyrene/butadiene/styrene block copolymers (SBS), styrene/ethylene-butene/ Styrene block copolymer (SEBS), polystyrene/isoprene/styrene block copolymer (SIS), polystyrene/isoprene/styrene block copolymer (SIS), polystyrene Ethylene/ethylene-propylene/styrene block copolymer (SEPS), polystyrene/ethylene-propylene block copolymer (SEP), and the like.
  • SBS polystyrene/butadiene/styrene block copolymers
  • SEBS styrene/ethylene-butene/ Styrene block copolymer
  • SIS polys
  • phase regions in the matrix of these materials which are formed by the soft segment and the hard segment of the molecular chain.
  • the soft and hard segments are in the viscous flow state and the glass state at normal temperature, but the hard segment restricts the soft segment flow, and the material exhibits high elasticity; At high temperatures, the soft and hard segments are in a viscous flow state, and the materials as a whole exhibit thermoplasticity, which makes them often used to prepare blending modified materials.
  • wire and cable covered insulation materials, bicycle solid tires is one of its most widely used applications.
  • a styrenic copolymer used as a wire and cable material or a solid tire must have good solvent resistance.
  • the styrene copolymer is a non-polar linear macromolecule with poor solubility. When it encounters a solvent such as gasoline, toluene or cyclohexane, it dissolves rapidly and the mechanical properties are greatly reduced and cannot be used. It is known that molecular chain cross-linking is the best method for improving the solvent resistance of a polymer, but the styrene-based copolymer has no active groups on its molecular chain, and cross-linking bonds cannot be formed between the molecular chains.
  • the hydroxystyrene copolymer has hydroxyl groups in the molecular chain and has high reactivity and can participate in cross-linking reaction.
  • Maruzen oil has used free radical polymerization method to prepare poly-p-hydroxybenzene with vinyl phenol as monomer.
  • Ethylene (US 4028340), Hoechst Celanese Company used the same method to prepare polyhydroxystyrene (US 5264528) with p-acetoxystyrene as a monomer. Both of the obtained products have a wide molecular weight and a complicated post-treatment process. And it is used as a styrene copolymer for wire and cable materials and solid tires. In addition to being solvent resistant, it needs to be able to be processed twice. Conventional chemical crosslinking improves its resistance to solvents, but it loses its ability to be overmolded.
  • the invention firstly provides a preparation method of a styrene crosslinked copolymer: a styrene copolymer having a furyl group and a polyfunctional maleimide derivative are obtained by solution polymerization or melt polymerization;
  • the solution polymerization is: dissolving a furan-based styrene copolymer in an organic solvent to prepare a copolymer solution having a concentration of not more than 30% by weight, and further adding a polymerization inhibitor, a polyfunctional maleimide derivative, The reaction is carried out at 80 to 140 ° C for 6 to 24 hours, and the product is precipitated and dried.
  • the melt polymerization is carried out by sequentially adding a polymerization inhibitor and a polyfunctional maleimide derivative to a furanyl group-containing styrene copolymer, and kneading at 170 to 240 ° C for 15 to 120 minutes, followed by cooling.
  • the styrene-based copolymer and the bismaleimide derivative having a furyl group are used in an amount sufficient to completely react the maleimide group;
  • the furan-based styrene copolymer is prepared by dissolving a hydroxyl group-containing styrene copolymer in an organic solvent to obtain a solution of a hydroxyl group-containing styrene copolymer, and sequentially adding a catalyst and a furanyl group-containing copolymer.
  • the active monomer is reacted at 20 to 50 ° C for 2 to 6 hours. After the reaction is completed, the product is precipitated with water and/or alcohol, and dried;
  • furanyl-containing reactive monomer is any one of furan derivatives capable of reacting directly or indirectly with a hydroxyl group; a molar ratio of a furyl-containing reactive monomer to a hydroxyl group-containing styrene copolymer 0.5 to 3:1;
  • the catalyst is any one or more of a pyridine, a pyridine derivative, a tertiary amine, a carbodiimide derivative, and an organotin compound, and the molar ratio of the catalyst to the reactive monomer having a furyl group is 0.001 to 5:1. ;
  • the hydroxyl group-containing styrene copolymer has a number average molecular weight of from 1,000,000 to 500,000.
  • the hydroxyl group-containing styrene copolymer has a number average molecular weight of 50,000 to 500,000.
  • the hydroxy structural unit in the hydroxyl group-containing styrene copolymer accounts for 0 ⁇ P ⁇ 33%, preferably 3 ⁇ P ⁇ 25%, of all structural units in the copolymer; and/or
  • the concentration of the solution of the hydroxyl group-containing styrene copolymer is not more than 30%; and/or the furan group-containing active monomer is any one of furoyl chloride, furancarboxylic acid, decyl alcohol and decylamine;
  • the molar ratio of the furanyl-containing reactive monomer to the hydroxyl group in the hydroxyl group-containing styrene copolymer is from 1 to 2:1.
  • the concentration of the hydroxyl group-containing styrene copolymer solution is 10 to 30% by weight.
  • the number of said styrenic copolymer with furyl-average molecular weight M n 01,000 ⁇ M n ⁇ 120 million; the Preferably, the number of said styrenic copolymer with furyl-average molecular weight M n 5 10,000 ⁇ M n ⁇ 850,000.
  • the structural unit of the styrene derivative having a furyl group accounts for 0 ⁇ N ⁇ 75%, preferably 5% ⁇ N ⁇ 55%, of all structural units in the copolymer.
  • the organic solvent is selected from any one of an alkane, a halogenated hydrocarbon, an ether, and an aromatic hydrocarbon solvent.
  • the organic solvent is selected from the group consisting of Any of cyclohexane, dichloromethane, dichloroethane, chloroform, tetrahydrofuran, and toluene.
  • the polyfunctional maleimide derivative contains two or more maleimide functional groups, preferably N,N'-(4,4'-methylene diphenyl Bismaleimide, N,N'-(1,4-phenylene) bismaleimide, 1,2-bis(maleimidoethoxy)ethane, N , N'-m-phenylene bismaleimide, 1,2-bis(maleimide)ethane, 1,4-bis(maleimido)butane, 1,6-di (Maleimido)hexane.
  • maleimide functional groups preferably N,N'-(4,4'-methylene diphenyl Bismaleimide, N,N'-(1,4-phenylene) bismaleimide, 1,2-bis(maleimidoethoxy)ethane, N , N'-m-phenylene bismaleimide, 1,2-bis(maleimide)ethane, 1,4-bis(maleimido)butane, 1,6-di (Maleimido)hexan
  • the molar ratio of the maleimide group to the furanyl group-containing styrene copolymer in the polyfunctional maleimide derivative is from 0.1 to 1:1.
  • the organic solvent is a solvent capable of simultaneously dissolving a furanyl group-containing styrene copolymer and a polyfunctional maleimide derivative, preferably toluene, xylene, tetrahydrofuran, dichloro Methane, chloroform; and/or the furanyl group-containing styrene copolymer solution has a mass concentration of 10 to 20%.
  • the polymerization inhibitor is one or more of a phenol compound, a quinone compound, and an oxynitride; and/or the polymerization inhibitor and the polyfunctional maleimide derivative
  • the molar ratio is 0 to 2:100.
  • the method for preparing the hydroxyl group-containing styrene copolymer comprises the following steps:
  • a monomer containing a structure of the formula I and / or the formula II and other vinyl monomers are prepared by anionic polymerization or cationic polymerization;
  • the copolymer obtained in the step (1) is dissolved in a solvent to form a copolymer solution, and then mixed with alkaline water, and hydrolyzed at 30 to 100 ° C for 1 to 12 hours to precipitate a copolymer, which is dried to obtain a hydroxyl group.
  • Styrene copolymer
  • R 1 and R 2 are each independently selected from C 1 - 12 alkyl, C 1 - 12 cycloalkyl, C 6 - 12 aryl, C 1 - 12 heteroaryl, C 1 - 12 heterocycloalkane a group wherein the alkyl group, cycloalkyl group, aryl group, heterocyclic aryl group, heterocycloalkyl group may be further selected from 1 to 4 independently selected from C 1 -6 alkyl groups, C 1 -6 cycloalkyl groups, C Substituted with 1 to 6 alkoxy groups, C 1 -6 alkylamino groups, C 1 -6 alkyl ester groups, and C 1 -6 alkanoyl groups;
  • the other vinyl monomer is one or more of an olefin monomer capable of anionic or cationic polymerization with a styrene monomer;
  • the anionic polymerization comprises the steps of adding a monomer having the structure of the formula I and/or formula II and other vinyl monomers to a system containing an activator or a solvent by a stepwise addition or a one-time addition. Mixing uniformly, further adding an initiator to polymerize at 25-90 ° C for 30-180 minutes, hydrogenation or non-hydrogenation after termination of the reaction, and finally removing the solvent to obtain a copolymer containing the structural unit of formula I and / or formula II;
  • the activator described in the anionic polymerization is a polar compound containing oxygen and/or nitrogen but no active hydrogen
  • the solvent is any solvent capable of simultaneously dissolving the monomer
  • the initiator is an alkyl metal compound, an alkoxy group. Any one of the base metal compounds;
  • the cationic polymerization comprises the steps of adding a monomer having the structure of the formula I and/or formula II and other vinyl monomers to a halogenated hydrocarbon and/or an alkane solvent by stepwise or one-time feeding.
  • the mixture is uniformly mixed, the temperature is lowered to below 0 ° C, and then the Lewis acid initiator is added, the polymerization time is not more than 1 hour, and after the reaction is terminated, hydrogenation or non-hydrogenation is carried out, and finally a copolymer containing the structural unit of the formula I and / or the formula II is obtained.
  • R 1 and R 2 are each independently selected from a C 1 -8 alkyl group, a C 1 -8 cycloalkyl group, a C 6 -8 aryl group, a C 1 -8 heterocyclic aryl group, and C 1 -8 Heterocycloalkyl; preferably, R 1 and R 2 are each independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl.
  • the other vinyl monomer is styrene, ⁇ -methylstyrene, isobutylene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, 1,3 One or more of pentadiene and isoprene.
  • the mass fraction N of the monomer having the structure represented by the formula I and/or the formula II is 0 ⁇ N ⁇ 33%, preferably 3 ⁇ N ⁇ 25%.
  • the mass concentration of the monomer in the reaction system is not more than 15%; and/or, in the designed molecular weight, the molar amount of the initiator is 1 to 1.25 times the theoretical amount; and/or the initiator
  • the molar ratio to the activator is from 1:0.02 to 20, preferably from 1:0.07 to 17.
  • the activator is one or more of tetrahydrofuran, dioxane, tetrahydrofurfuryl ethyl ether, N,N-dimethyltetrahydrofurfurylamine, and dimethylformamide.
  • the solvent is cyclohexane; and/or the initiator is any one of n-butyllithium, sec-butyllithium, and tert-butyllithium.
  • the mass concentration of the monomer in the reaction system is not more than 15%; and/or, in the designed molecular weight, the molar amount of the initiator is 1-1.5 times the theoretical amount.
  • the solvent is one or more of monochloromethane, dichloromethane, dichloroethane, n-hexane; and/or the initiator is aluminum trichloride or dichloroethyl Any one of aluminum, diethylaluminum chloride, triethylaluminum, tin tetrachloride, and titanium tetrachloride.
  • the copolymer solution has a mass concentration of not more than 15%; and/or the solvent is any copolymer capable of dissolving the structural unit containing the formula I and/or the formula II and is not mixed with the alkaline water.
  • a solvent for the reaction; and/or a mass ratio of the copolymer solution to the alkali water is from 100 to 20:1; and/or the aqueous alkali solution is composed of an alkali metal hydroxide, a phase transfer catalyst and water; an alkali metal hydrogen
  • the mass concentration ⁇ of the oxide ranges from 0 ⁇ ⁇ ⁇ 55%; the mass concentration ⁇ of the phase transfer catalyst ranges from 0 ⁇ ⁇ ⁇ 15%.
  • the solvent is any one of cyclohexane, n-hexane, n-heptane, n-octane, toluene, and xylene; and/or the alkali metal hydroxide is Any one of lithium hydroxide, potassium hydroxide, and sodium hydroxide, and the mass concentration ⁇ ranges from 25 ⁇ ⁇ ⁇ 50%; and/or the phase transfer catalyst is a quaternary ammonium salt, an alkyl ammonium halide, Any one of a tertiary amine, a quaternary ammonium base, a quaternary phosphonium salt, and a cyclic crown ether, and the mass concentration ⁇ in the alkaline water is in the range of 5 ⁇ ⁇ ⁇ 15%; preferably, the phase transfer catalyst is Alkyl ammonium halides.
  • the invention also provides a styrene cross-linked copolymer containing a reversible cross-linking bond of furanyl group and maleimide-based diene addition, and swelling of the styrene-based cross-linked copolymer in toluene The degree is 3.8 to 34.2.
  • the present invention also provides the use of the above styrene-based crosslinked copolymer, which can be used for preparing wire and cable materials and tires which are resistant to solvents and can be repeatedly formed.
  • the reversible cross-linking bond described in the present invention means that the cross-linking bond formed by the reaction of the reactant can be broken under certain conditions, and the cross-linking bond is a reversible cross-linking bond.
  • the minimum carbon atom content of the hydrocarbon group represented by the prefix and the maximum value e.g., the prefix C ab alkyl, C ab cycloalkyl, C ab aryl, C ab heterocyclic aryl, heterocycloalkyl C ab Respectively denotes any alkyl group, cycloalkyl group, aryl group, heterocyclic aryl group or heterocycloalkyl group having from "a" to "b" carbon atoms.
  • C 1-4 alkyl means an alkyl group having 1 to 4 carbon atoms.
  • the C ab alkoxy group, the C ab alkyl ester group, the C ab alkyl group, and the C ab acyl group respectively mean that the alkyl group having “a” to “b” carbon atoms is bonded to the corresponding oxygen atom, ester group, amino group, acyl group.
  • the resulting group The alkyl group having “a” to “b” carbon atoms is bonded to the corresponding oxygen atom, ester group, amino group, acyl group.
  • the present invention has the following advantages:
  • the styrene-based copolymer with reversible cross-linking bond prepared by the invention overcomes the shortcomings of poor solvent resistance of the existing linear styrene macromolecular materials, and overcomes the secondary processing capability of the existing chemically cross-linked styrene. Shortcomings.
  • the styrene-based copolymer prepared by the invention with reversible cross-linking bonds has better solvent resistance and secondary processing capability.
  • the present invention provides a styrene-based copolymer having a furyl group and a process for producing the same.
  • the furan-based styrene copolymer prepared by the invention can be used for preparing a styrene copolymer material with reversible cross-linking bonds, overcomes the shortcomings of the solvent resistance of the existing linear styrene macromolecular materials, and overcomes the existing chemistry.
  • Crosslinked styrene has the disadvantage of no secondary processing capability.
  • the furan-based styrene-based copolymer prepared by the present invention can be used for preparing a styrene-based copolymer material having good solvent resistance and secondary molding ability.
  • the present invention discloses a novel process for preparing a hydroxy group-containing styrene copolymer.
  • the invention adds a functional comonomer in the polymerization process for preparing the styrene copolymer, and simplifies the preparation process of the hydroxystyrene copolymer compared with the prior art, the post-treatment is simple, the reaction is fast and efficient, and the prepared
  • the hydroxyl group-containing styrene copolymer elastomer has the advantages of high molecular weight, narrow molecular weight distribution, and adjustable and controllable hydroxyl structural unit, and is very suitable for industrial production.
  • Figure 1 is a flow chart for the preparation of a furanyl styrene-based copolymer.
  • FIG. 2 Fourier infrared spectrum of a hydroxyl group-containing styrene copolymer (Sample 1-2).
  • Figure 4 is a 1 H NMR chart of a hydroxy group-containing styrene copolymer (Sample 1-2).
  • Figure 5 is a 1 H NMR chart of a furanyl styrene copolymer (prepared in Sample 1-2).
  • Fig. 6 Solvent resistance of the hydroxy group-containing styrene copolymer (1) and the reversible crosslinkable styrene copolymer material (2).
  • Figure 7 Depolymerization of a styrenic copolymer material containing a reversible crosslink.
  • the reagents used in the examples of the present invention mainly include: 4-vinylbenzyl acetate, 4-acetoxystyrene, n-butyllithium (1.6M), styrene, decyl alcohol, and diphenylmethane diisocyanate.
  • 4-vinylbenzyl acetate 4-acetoxystyrene, n-butyllithium (1.6M), styrene, decyl alcohol, and diphenylmethane diisocyanate.
  • aluminum trichloride, ethylaluminum dichloride, diethylaluminum dichloride, furanyl chloride and decylamine were purchased from Aladdin reagent company
  • tin tetrachloride (1M) was purchased from Acros reagent company, toluene II.
  • Isocyanates were purchased from TCI Reagents Inc., both of which are conventional commercial products.
  • the obtained copolymer was subjected to 1H NMR test using a Bruker AV 600 MHz nuclear magnetic resonance apparatus using CDCl 3 as a solvent.
  • the molecular weight was tested using a Water 1525 gel permeation chromatograph, tetrahydrofuran as the eluent (1 ml/min), and standard polystyrene as a reference.
  • the sample was immersed in toluene, soaked for 24 hours. After removal, the solvent on the surface was quickly wiped off, and weighed, and the weight ⁇ 2 was recorded. After vacuum drying, the weight was recorded as ⁇ 3, and the initial mass of the sample was ⁇ 1.
  • the swelling degree was calculated according to the following formula. (SD) and gel content (GD):
  • the tensile strength of the test specimen was tested according to the ASTM D-638-08 test standard using an INSTRON 5567 universal material testing machine at a tensile speed of 50 mm/min.
  • the 1 L polymerization vessel was evacuated and replaced with high-purity nitrogen three times, and 650 ml of purified cyclohexane was first added to design a solid content of 10%.
  • Table 1 and Table 2 first add the first 4-methylbenzyl acetate and styrene mixed monomer, 0.25ml tetrahydrofuran, stir, then add n-butyl lithium solution according to Table 2 ( The concentration was 0.5 M), and the reaction was carried out at 40 ° C for 1 hour, then butadiene was added, the reaction was continued for 1 hour, and finally the third stage of 4-vinylbenzyl acetate and styrene mixed monomer was further added, and the reaction was further carried out for 1 hour.
  • the polymerization liquid was pressurized into a hydrogenation reactor, and hydrogen was introduced to terminate the reaction. After half an hour, 1 mL of a concentration of 0.02 mol/L methyl o-methylbenzoate, 30 mg of titanium dichloride, and hydrogen gas were introduced thereto, and the temperature was controlled at 70 ° C and a pressure of 2 MPa. After the reaction was completed for 6 hours, the material was discharged.
  • the styrene-ethylene/butylene-styrene block copolymer having different hydroxyl contents can be prepared by adjusting the content of hydroxyl groups in the monomer, thereby preparing styrene copolymers having different furan content. Things.
  • the crosslinked styrene copolymer prepared by crosslinking a furyl-containing styrene copolymer with N,N'-(4,4'-methylenediphenyl)bismaleimide improves the polymerization well.
  • the solvent resistance of the styrene copolymer, in which the solvent resistance of the samples 1-1, 1-2 is better after crosslinking.
  • Fig. 6 (1) shows the results of the solubility test of the hydroxy group-containing styrene copolymer (sample 1-2) in toluene. The results indicate that toluene can dissolve the hydroxyl group-containing styrene copolymer.
  • the furyl-containing styrene copolymer is reacted with N,N'-(4,4'-methylenediphenyl) bismaleimide at 100 ° C to form a styrene containing a reversible crosslink.
  • the copolymer material was placed in a toluene solvent.
  • the product was dissolved in n-octane to form a solution, 50 ml of a 40 wt% aqueous solution of sodium hydroxide was added, and 5 wt% of cetyltrimethylammonium bromide was added, and the mixture was hydrolyzed at 70 ° C for 1 hour, and then the reaction solution was slowly injected.
  • the mixture is boiled in a 10% sodium hydroxide boiling water at a concentration of 100 ° C to remove the solvent and other impurities, and the product is precipitated and dried to obtain a hydroxylated star-type styrene-ethylene/butylene-styrene block copolymer.
  • the 1 L polymerizer was evacuated and replaced with high purity nitrogen three times. First, 650 ml of purified cyclohexane was added to design a solid content of 15%, and then the formulations were added according to the formulas of Tables 6 and 7.
  • the product is dissolved in n-heptane or n-hexane, 50 ml of a 30 wt% aqueous solution of sodium hydroxide is added, 15 wt% of tetrabutylammonium bromide is contained in alkali water, and hydrolyzed at 60 ° C for 3 hours, and finally methanol is added to the reaction liquid.
  • the product was precipitated and dried to obtain a styrene-ethylene/propylene-styrene block copolymer having a hydroxyl group.
  • Table 7 The synthetic formula and process and molecular weight test results are shown in Table 7.
  • furan methanol was slowly added dropwise to toluene diisocyanate, the amount of furan methanol and isocyanate was controlled to be 1.1:1, dibutyltin dilaurate was added at 0.1% by mole of furan methanol, and reacted at 50 ° C for 2 hours to obtain a terminal.
  • the base is an isocyanate group-containing furan.
  • the 1 L polymerization vessel was evacuated and replaced with high-purity nitrogen three times, and 650 ml of purified cyclohexane was first added to design a solid content of 10%.
  • 11.6 g of 4-vinylbenzylcyclopentylformate (7.1% by mole of monomer), 4.17 g of styrene, 1.2 g of ⁇ -methylstyrene, 0.59 mol of butadiene, 0.234 mmol of N, N were added in that order.
  • -Dimethyltetrahydrofurfurylamine stirring, adding 2.08 ml of sec-butyllithium solution (concentration: 0.5 M), and reacting at 60 ° C for 2 hours. Finally, the reaction was hydraulically introduced into the stop vessel, and ethanol was added to terminate the reaction.
  • styrene- ⁇ -methylstyrene-butadiene random copolymer having a hydroxyl group, a number average molecular weight of about 48,000, a molecular weight distribution width of 1.17, and a hydroxyl group-containing structural unit accounting for 15.4. %.
  • guanamine was slowly added dropwise to diphenylmethane diisocyanate, dibutyltin dilaurate was added in an amount of 0.5% by mole of guanamine, and the amount of guanamine and isocyanate was controlled to be 1.05:1, and reacted at 40 ° C for 2 hours to obtain a terminal isocyanate.
  • a tetrahydrofuran solution (mass concentration: 20%) of a styrene- ⁇ -methylstyrene-butadiene random copolymer containing 5 g of a hydroxyl group was added dropwise to the terminal isocyanate-based furan, and reacted at 50 ° C for 2 hours, and distilled water was added thereto. The product was precipitated and dried by filtration to obtain a furyl-containing styrene- ⁇ -methylstyrene-butadiene random copolymer.
  • the 1 L polymerization vessel was evacuated and replaced with high-purity nitrogen three times, and 650 ml of purified cyclohexane was first added to design a solid content of 10%. Then, 13.31 g of p-tetravinylbenzyl (3-phenyl)propionate (9.0% by mole of monomer), 5.2 g of styrene, 31 g of isoprene, and 0.30 mmol of dimethylformamide were added. After stirring, 1.66 ml of n-butyllithium solution (concentration: 0.5 M) was added, and the reaction was carried out at 40 ° C for 3 hours. Finally, the reaction was hydraulically introduced into the stop vessel, and ethanol was added to terminate the reaction.
  • the product was dissolved in 1 L of toluene, 30 ml of a 45 wt% aqueous solution of potassium hydroxide was added, 5 wt% of tetrabutylammonium chloride was added to the alkali water, and hydrolysis was carried out at 50 ° C for 8 hours. Finally, methanol was added to the reaction solution to precipitate the product. The mixture was washed with water and dried to obtain a styrene-isobutylene random copolymer having a hydroxyl group, a molecular weight of 162,000, a molecular weight distribution width of 5.6, and a hydroxyl group-containing structural unit in an amount of 8.6 wt%.
  • a styrene-isobutylene random copolymer containing 5 g of a hydroxyl group was dissolved in chloroform, and a furyl-containing styrene-isobutylene random copolymer was synthesized according to the method of Example 5.
  • the amount of furoyl chloride was 9 mmol, and the amount of DAMP was unchanged. 0.045 mol of pyridine was added.
  • the solid content was controlled to 8%.
  • the reaction solvent was n-hexane, 7.81 g of styrene, 4.4 g of 4-vinylbenzyl acetate (4.2% by mole of the monomer), and 27.8 g.
  • the reaction temperature is -30 ° C
  • the initiator is 5.5 ml 50mmol / L titanium chloride in dichloromethane solution
  • the reaction time is 45 minutes
  • other conditions are the same, and then hydrolyzed to obtain hydroxy-containing styrene-different A pentadiene random copolymer having a molecular weight of 159,000, a molecular weight distribution width of 6.2, and a hydroxyl group-containing structural unit accounting for 8.6 wt%.
  • a styrene-isoprene random copolymer containing furyl group was synthesized by dissolving 5 g of a hydroxystyrene-isoprene random copolymer in cyclohexane as in Example 5, and the molar amount of furoyl chloride was used. As 9 mmol, the amount of DAMP was unchanged, and 0.045 mol of pyridine was slowly added.
  • the solid content was controlled to 10%, and 500 g of methyl chloride (precooled to -80 ° C), 15 g of 4-vinylbenzyl acetate (12% by mole of monomer), and a molar ratio of 35 g were sequentially added to a 1 L polymerization vessel.
  • a 20:1 mixture of isobutylene/3 methyl-1-butene was stirred and mixed uniformly, and cooled to about -100 °C.
  • 11 ml of a dichloromethane solution containing 19.5 mmol/L of aluminum trichloride was slowly added dropwise to the reaction vessel, and the polymerization temperature was maintained.
  • the product was dissolved in 1 L of xylene, 40 ml of a 25 wt% aqueous solution of potassium hydroxide was added, and 5 wt% of tetradecyltrimethylammonium bromide was added to the alkali water, and the mixture was hydrolyzed at 35 ° C for 12 hours, and finally added to the reaction liquid.
  • Methanol the product is precipitated, washed with water, and dried to obtain a styrene-isobutylene-3-methyl-1-butene random copolymer having a hydroxyl group, a molecular weight of 266,000, a molecular weight distribution width of 4.5, and a hydroxyl group-containing structural unit.
  • the proportion is 24wt%.
  • the product was dissolved in 1 L of cyclohexane, 30 ml of a 30 wt% aqueous solution of sodium hydroxide was added, and 5 wt% of trioctylmethylammonium bromide was added to the alkali water, and hydrolyzed at 45 ° C for 9 hours, and finally added to the reaction liquid. Ethanol, the product is precipitated, washed with water, and dried to obtain a styrene-isobutylene-4-methyl-1-pentene random copolymer having a hydroxyl group, a molecular weight of 118,000, a molecular weight distribution width of 4.3, and a hydroxyl group-containing structural unit. The ratio is 8.2 wt%.
  • the reactor was charged with 18.75 ml of a dichloromethane solution containing 20 mmol/L of tin tetrachloride, and the reaction temperature was maintained for 1 hour, and then 3 ml of a precooled methanol solution containing 0.2 mol/L of potassium hydroxide was added to terminate the polymerization.
  • the reaction solvent was removed, washed with water, and dried to obtain a styrene-isobutylene-1,3-pentadiene random copolymer containing a p-4-acetoxystyrene structural unit.
  • the product was dissolved in 1 L of cyclohexane, 20 ml of a 50 wt% aqueous solution of sodium hydroxide was added, and 5 wt% of tetrabutylammonium bromide was contained in alkali water, and hydrolyzed at 30 ° C for 12 hours, and the reaction liquid was poured into boiling water to precipitate.
  • the product was obtained, and after drying, a styrene-isobutylene-1,3-pentadiene random copolymer having a hydroxyl group was obtained, a molecular weight of 292,000, a molecular weight distribution width of 3.8, and a ratio of a hydroxyl group-containing structural unit of 10.02% by weight.
  • the present invention was subjected to solvent resistance (Fig. 6) and depolymerization test (Fig. 7) of the reversible crosslinkable styrene copolymer material obtained in Samples 1-2 of Example 1.
  • the hydroxyl group-containing styrene copolymer (Sample 1-2) was quickly dissolved in toluene at normal temperature as shown in Fig. 6 (1).
  • Furanyl styrene copolymer reacts with N,N'-(4,4'-methylenediphenyl) bismaleimide at 100 ° C to form a styrene copolymer material containing a reversible crosslink bond
  • the obtained material was placed in a toluene solution, and after standing at room temperature for 24 hours, the material could not be dissolved in toluene, as shown in Fig. 6 (2) and the lower left diagram of Fig. 7, indicating that the furyl-based styrene copolymer was cross-linked.
  • a styrene copolymer having a furan group is prepared by directly or indirectly reacting a reactive monomer having a furyl group with a styrene copolymer having a hydroxyl group.
  • the furanyl-containing styrene copolymer prepared by the invention can be reacted with maleimide to prepare a copolymer material containing a reversible crosslink bond, and the copolymer material exhibits good solvent resistance and has secondary processing ability. It is expected to be applied to recyclable wire and cable covering materials, bicycle tires and other fields, which is of great industrial value.
  • the proportion of the furanyl structural unit on the furanyl styrene copolymer can be controlled by a specific polymerization process, thereby changing the degree of crosslinking of the reversible crosslinked copolymer material to meet the needs of different application fields.

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Abstract

公开了一种带可逆交联键的苯乙烯类共聚物及其制备方法和用途。首先合成带羟基的苯乙烯类共聚物，然后与呋喃衍生物单体发生反应制成带呋喃基的苯乙烯类共聚物，再与多官能度马来酰亚胺衍生物反应生成带可逆交联键的苯乙烯类共聚物，改善了苯乙烯类共聚物材料的耐溶剂性能。提供的带可逆交联键的苯乙烯类共聚物材料中的可逆交联键可在高温下断开，材料具有二次加工性能，可以反复使用。

Description

[根据细则37.2由ISA制定的发明名称]　带可逆交联键的苯乙烯类共聚物及其制备方法 技术领域
本发明属于苯乙烯类共聚物，具体涉及一种带可逆交联键的苯乙烯类共聚物及其制备方法。
背景技术
苯乙烯类共聚物是一类在分子链内存在聚苯乙烯链段的聚合物材料，例如聚苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/乙烯-丁烯/苯乙烯嵌段共聚物(SEBS)、聚苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)、聚苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)、聚苯乙烯/乙烯-丙烯/苯乙烯嵌段共聚物(SEPS)、聚苯乙烯/乙烯-丙烯嵌段共聚物(SEP)等。这些材料基体内存在由分子链软段和硬段相互贯穿而成的相区，常温下软、硬链段分别处于粘流态、玻璃态，但硬段限制软段流动，材料呈现高弹性；高温下软、硬链段均处于粘流态，材料整体呈现热塑性，这一特性使得它们常被用于制备共混改性专用料。其中，电线电缆包覆绝缘材料、自行车实心轮胎就是其最广泛的应用之一。
用作电线电缆料、实心轮胎的苯乙烯类共聚物，必须具有良好的耐溶剂性。苯乙烯类共聚物为非极性线性大分子，耐溶性较差，遇到汽油、甲苯、环己烷等溶剂，则快速溶解，力学性能大幅度下降，无法使用。众所周知，分子链间交联是改善聚合物耐溶剂性最好的方法，但所述的苯乙烯类共聚物分子链上没有活性基团，分子链间无法形成交联键。目前，有一些关于苯乙烯类共聚物改性的方法的报道，例如磺化((Synthesis and characterization of sulfonated poly(styrene-b-(ethylene-ran-butylene)-b-styrene)/(strontium titanate)nanocomposites.European Polymer Journal,2013,49:1446)、乙酰化、羧化(Synthesis of novel triblock copolymers containing hydrogen-bond interaction groups via chemical modification of hydrogenated poly(styrene-block-butadiene-block-styrene).Macromolecules,1995,28:8702)、氯甲基化(Studies on performing chloromethylation reaction for polystyrene by micellar catalysis in aqueous surfactant solutions.Chemical Engineering and Processing,2008,47:852)、马来酸酐接枝(Improved compatibility between polyamide and polypropylene by the use of maleic anhydride grafted SEBS.Polymer,1998,39:6705)等。其中，磺化、乙酰化、马来酸酐接枝等方法报道较多，所得的改性苯乙烯类共聚物分子链上虽接上极性基团，但没有反应活性，无法与其他活性单体或聚合物反应。氯甲基化苯乙烯共聚物分子链上的氯甲基具有反应活性，可以进一步改性得到满足各种应用的聚合物，但反应过程复杂，成本高昂。羟基苯乙烯共聚物的分子链上含羟基，反应活性高，可以参与交联反应。Maruzen oil公司曾采用自由基聚合方法以乙烯基苯酚为单体制备聚对羟基苯乙烯(US 4028340)，Hoechst Celanese公司用相同方法以对乙酰氧基苯乙烯为单体制备聚羟基苯乙烯(US 5264528)，两者所得产物的分子量皆较宽，后处理过程复杂。并且用作电线电缆料、实心 轮胎的苯乙烯类共聚物，除了能耐溶剂，还需能进行二次加工。常规化学交联虽能改善其耐溶剂，但使其失去二次成型的能力。
发明内容
本发明的目的在于提供一种带可逆交联键的苯乙烯类共聚物及其制备方法和用途。
本发明首先提供了一种苯乙烯类交联共聚物的制备方法：带呋喃基的苯乙烯类共聚物与多官能度马来酰亚胺衍生物通过溶液聚合或熔融聚合制得；
所述的溶液聚合为：将带呋喃基的苯乙烯类共聚物溶于有机溶剂中制备浓度不超过30wt％的共聚物溶液，再加入阻聚剂、多官能度马来酰亚胺衍生物，在80～140℃反应6～24h，沉淀出产物，烘干即得；
所述的熔融聚合为：向带呋喃基的苯乙烯类共聚物中依次加入阻聚剂、多官能度马来酰亚胺衍生物，于170～240℃下混炼15～120分钟，冷却即得；
其中，带呋喃基的苯乙烯类共聚物和双马来酰亚胺衍生物的用量为能使马来酰亚胺基完全反应的量；
所述的带呋喃基的苯乙烯类共聚物制备方法为：将带羟基的苯乙烯类共聚物溶解到有机溶剂中得到带羟基的苯乙烯类共聚物的溶液，依次加入催化剂、含呋喃基的活性单体，20～50℃反应2～6h，反应结束后，用水和/或醇沉淀出产物，烘干即得；
其中，所述含呋喃基的活性单体是能与羟基直接或间接反应的呋喃衍生物中的任意一种；含呋喃基的活性单体与含羟基的苯乙烯类共聚物中羟基的摩尔比为0.5～3:1；
所述催化剂为吡啶、吡啶衍生物、叔胺、碳二亚胺衍生物、有机锡化合物中的任意一种或多种，催化剂与带呋喃基的活性单体的摩尔量比0.001～5:1；
所述带羟基的苯乙烯类共聚物数均分子量为0.1万～50万。
进一步地，所述带羟基的苯乙烯类共聚物数均分子量为5万～50万。
进一步地，所述带羟基的苯乙烯类共聚物中羟基结构单元占共聚物中所有结构单元的质量分数P为0<P≤33％，优选为3≤P≤25％；和/或，所述带羟基的苯乙烯类共聚物的溶液的质量浓度不超过30％；和/或，所述带呋喃基的活性单体为呋喃甲酰氯、呋喃甲酸、糠醇、糠胺中的任意一种；和/或，所述含呋喃基的活性单体与含羟基的苯乙烯类共聚物中羟基单元的摩尔比为1～2:1。
进一步地，所述带羟基的苯乙烯类共聚物溶液的浓度为10～30wt％。
进一步地，所述带呋喃基的苯乙烯类共聚物数均分子量M n为0.1万<M n<120万；优选地，所述带呋喃基的苯乙烯类共聚物数均分子量M n为5万≤M n≤85万。
进一步地，所述带呋喃基的苯乙烯衍生物结构单元占共聚物中所有结构单元的质量分数N为0<N≤75％，优选地，5％≤N≤55％。
进一步地，所述带呋喃基的苯乙烯类共聚物的制备方法中，有机溶剂选自烷烃、卤代烃、醚、芳香烃溶剂中的任意一种，优选地，所述的有机溶剂选自环己烷、二氯甲烷、二氯乙烷、三氯甲烷、四氢呋喃、甲苯中的任意一种。
进一步地，所述的多官能度马来酰亚胺衍生物中含有2个或2个以上的马来酰亚胺官能团，优选为N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺、N,N'-(1,4-亚苯基)双马来酰亚胺、1,2-双(马来酰亚胺基乙氧基)乙烷、N,N'-间苯撑双马来酰亚胺、1,2-二(马来酰亚胺)乙烷、1,4-双(马来酰亚胺基)丁烷、1,6-二(马来酰亚胺基)己烷。
进一步地，所述的多官能度马来酰亚胺衍生物中马来酰亚胺基与带呋喃基的苯乙烯类共聚物中呋喃基的摩尔比为0.1～1:1。
进一步地，所述溶液聚合过程中，有机溶剂为能同时溶解带呋喃基的苯乙烯类共聚物和多官能度马来酰亚胺衍生物的溶剂，优选为甲苯、二甲苯、四氢呋喃、二氯甲烷、三氯甲烷；和/或，所述的带呋喃基的苯乙烯类共聚物溶液的质量浓度为10～20％。
进一步地，所述的阻聚剂为酚类化合物、醌类化合物、氮氧化合物中的一种或多种；和/或，所述阻聚剂与多官能度马来酰亚胺衍生物的摩尔比为0～2:100。
进一步地，所述带羟基的苯乙烯类共聚物的制备方法包括以下步骤：
(1)含有式I和/或式II结构的单体与其他乙烯基单体通过阴离子聚合或阳离子聚合制备共聚物；
(2)将步骤(1)所得共聚物溶解到溶剂中形成共聚物溶液，再与碱水混合，于30～100℃下水解1～12h，沉淀出共聚物，烘干后即得带羟基的苯乙烯类共聚物；
Figure PCTCN2018093648-appb-000001
其中，R 1、R 2分别独立地选自C 1～ 12烷基、C 1～ 12环烷基、C 6～ 12芳基、C 1～ 12杂环芳基、C 1～ 12杂环烷基，其中所述烷基、环烷基、芳基、杂环芳基、杂环烷基可以进一步被1～4个独立选自C 1～ 6烷基、C 1～ 6环烷基、C 1～ 6烷氧基、C 1～ 6烷胺基、C 1～ 6烷酯基、C 1～ 6烷酰基的取代基取代；
所述的其他乙烯基单体为能与苯乙烯单体进行阴离子或阳离子聚合的烯烃单体中的一种或多种；
所述的阴离子聚合包括以下步骤：用分步加料或一次性加料方式，将具有式I和/或式II所示结构的单体和其他乙烯基单体加入到含有活化剂、溶剂的体系中混合均匀，再加入引发剂于25～90℃下聚合30～180分钟，反应终止后进行氢化或不氢化，最后脱除溶剂，得到含有式I和/或式II结构单元的共聚物；
其中，阴离子聚合中所述的活化剂为含氧和/或含氮的但不含活性氢的极性化合物，溶剂为任何能同时溶解单体的溶剂，引发剂为烷基金属化合物、烷氧基金属化合物中的任意一种；
所述的阳离子聚合包括以下步骤：用分步加料或一次性加料方式，将具有式I和/或式II所示结构的单体和其他乙烯基单体加入卤代烃和/或烷烃溶剂中混合均匀，降低温度至0℃以下，再加入Lewis酸引发剂，聚合时间不超过1小时，反应终止后进行氢化或不氢化，最后得到含有式I和/或式II结构单元的共聚物。
进一步地，所述R 1、R 2分别独立地选自C 1～ 8烷基、C 1～ 8环烷基、C 6～ 8芳基、C 1～ 8杂环芳基、C 1～ 8杂环烷基；优选地，所述R 1、R 2分别独立地选自甲基、乙基、丙基、异丙基。
进一步地，所述其他乙烯基单体为苯乙烯、α-甲基苯乙烯、异丁烯、3-甲基-1-丁烯、4-甲基-1-戊烯、丁二烯、1,3-戊二烯、异戊二烯中的一种或多种。
进一步地，步骤(1)中，所述具有式I和/或式II所示结构的单体的质量分数N为0<N≤33％，优选为3≤N≤25％。
进一步地，所述阴离子聚合中，反应体系中单体的质量浓度不超过15％；和/或，在设计分子量下，引发剂摩尔用量为理论用量的1～1.25倍；和/或，引发剂与活化剂的摩尔比为1:0.02～20，优选为1:0.07～17。
进一步地，所述阴离子聚合中，活化剂为四氢呋喃、二氧六环、四氢糠醇乙基醚、N,N-二甲基四氢糠胺、二甲基甲酰胺中的一种或多种；和/或，溶剂为环己烷；和/或，引发剂为正丁基锂、仲丁基锂、叔丁基锂中的任意一种。
进一步地，所述阳离子聚合中，反应体系中单体的质量浓度不超过15％；和/或，在设计分子量下，所述引发剂摩尔用量为理论用量的1-1.5倍。
进一步地，所述阳离子聚合中，溶剂为一氯甲烷、二氯甲烷、二氯乙烷、正己烷中的一种或多种；和/或，引发剂为三氯化铝、二氯乙基铝、一氯二乙基铝、三乙基铝、四氯化锡、四氯化钛中任意一种。
进一步地，步骤(2)中，所述共聚物溶液质量浓度不超过15％；和/或，所述溶剂为任何能溶解含有式I和/或式II结构单元的共聚物且不与碱水反应的溶剂；和/或，共聚物溶液与碱水的质量比为100～20:1；和/或，所述的碱水溶液由碱金属氢氧化物、相转移催化剂和水组成；碱金属氢氧化物的质量浓度ω的范围为0<ω≤55％；相转移催化剂的质量浓度δ的范围为0<δ≤15％。
进一步地，步骤(2)中，所述溶剂为环己烷、正己烷、正庚烷、正辛烷、甲苯、二甲苯中的任意一种；和/或，所述碱金属氢氧化物为氢氧化锂、氢氧化钾、氢氧化钠中的任意一种，且质量浓度ω的范围为25≤ω≤50％；和/或，所述相转移催化剂为季铵盐、烷基卤化铵、叔胺类、季铵碱类、季膦盐类、环状冠醚类中的任意一种，且在碱水中的质量浓度δ的范围为5≤δ≤15％；优选地，相转移催化剂为烷基卤化铵类。
本发明还提供了一种苯乙烯类交联共聚物，分子中含有呋喃基与马来酰亚胺基双烯加成得到的可逆交联键，苯乙烯类交联共聚物在甲苯中的溶胀度为3.8～34.2。
进一步地，它是以上述制备方法制备而得。
本发明还提供了上述苯乙烯类交联共聚物的用途，可用于制备耐溶剂且能反复成型加工的电线电缆料、轮胎。
本发明中所述的可逆交联键是指反应物反应生成的交联键在一定条件下可断开，该交联键即为可逆交联键。
碳氢基团中碳原子含量的最小值和最大值通过前缀表示，例如，前缀C a-b烷基、C a-b环烷基、C a-b芳基、C a-b杂环芳基、C a-b杂环烷基分别表示任何含“a”至“b”个碳原子的烷基、环烷基、芳基、杂环芳基、杂环烷基。例如，C 1-4烷基是指包含1～4个碳原子的烷基。
C a-b烷氧基、C a-b烷酯基、C a-b烷氨基、C a-b酰基分别是指含有“a”至“b”个碳原子的烷基与对应的氧原子、酯基、氨基、酰基相连得到的基团。
本发明与现有技术相比，具备以下优点：
(1)本发明制备的带可逆交联键的苯乙烯类共聚物克服了现有线性苯乙烯大分子材料耐溶剂性差的缺点，同时克服了现有化学交联的苯乙烯无二次加工能力的缺点。本发明制备带可逆交联键的苯乙烯类类共聚物既有较好的耐溶剂性能，又具有二次加工成型能力。
(2)本发明提供了一种带呋喃基的苯乙烯类共聚物及其制备方法。本发明制备的带呋喃基的苯乙烯类共聚物可用于制备具有可逆交联键的苯乙烯共聚物材料，克服了现有线性苯乙烯大分子材料耐溶剂性差的缺点，同时克服了现有化学交联的苯乙烯无二次加工能力的缺点。本发明制备的带呋喃基的苯乙烯类共聚物可用于制备耐溶剂性能好，同时具有二次成型能力的苯乙烯类共聚物材料。
(3)本发明公开了一种全新的制备带羟基的苯乙烯类共聚物的方法。本发明在制备苯乙烯类共聚物的聚合过程中，加入功能性共聚单体，与现有技术相比，简化了羟基苯乙烯共聚物的制备过程，后处理简单，反应快速高效，所制备的带羟基的苯乙烯类共聚物弹性体具有分子量高、分子量分布窄、羟基结构单元可调可控的优点，非常适合工业化生产。
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1含呋喃基苯乙烯类共聚物制备流程图。
图2带羟基的苯乙烯类共聚物(样品1-2)的傅里叶红外光谱。
图3带呋喃基的苯乙烯类共聚物(样品1-2制得)的傅里叶红外光谱。
图4带羟基的苯乙烯类共聚物(样品1-2)的 1H NMR图。
图5带呋喃基苯乙烯类共聚物(样品1-2制得)的 1H NMR图。
图6带羟基的苯乙烯类共聚物(1)和含可逆交联键的苯乙烯类共聚物材料(2)的耐 溶剂性。
图7含可逆交联键的苯乙烯类共聚物材料的解聚。
具体实施方式
本发明实施例所用的试剂主要有：4-乙烯苄基乙酸酯、对4-乙酰氧基苯乙烯、正丁基锂(1.6M)、苯乙烯、糠醇、二苯基甲烷二异氰酸酯均购置于Adamas试剂公司；三氯化铝、二氯乙基铝、一氯二乙基铝、呋喃酰氯、糠胺均购置于Aladdin试剂公司；四氯化锡(1M)购置于Acros试剂公司，甲苯二异氰酸酯购置于TCI试剂公司，均为常规市售产品。
以CDCl 3作为溶剂，用Bruker AV 600MHz核磁共振仪对所制得的共聚物进行1H NMR测试。
以氯仿为溶剂，在KBr盐片上涂膜后，采用Nieolet NEXUS670傅里叶红外光谱仪器进行红外测试。
分子量采用Water 1525型凝胶渗透色谱仪进行测试，四氢呋喃为淋洗液(1ml/min)，标准聚苯乙烯作为参比。
将样品浸入甲苯中，浸泡24小时，取出后迅速擦去表面的溶剂，并称量，记下重量ω2，真空烘干后重量记为ω3，样品的初始质量为ω1，按照如下公式计算溶胀度(SD)和凝胶含量(GD)：
Figure PCTCN2018093648-appb-000002
采用INSTRON 5567型万能材料测试机按照ASTM D-638-08测试标准测试样的拉伸强度，拉伸速度为50mm/min。
实施例1
(1)阴离子聚合制备带羟基的苯乙烯-乙烯/丁烯-苯乙烯线性嵌段共聚物
将1L聚合釜抽真空，用高纯氮气置换三次，先加入650ml纯化的环己烷，设计固含量10％。按表1和表2配比加料，先加入第一段的对4-乙烯苄基乙酸酯和苯乙烯混合单体、0.25ml四氢呋喃，开搅拌，再按表2加入正丁基锂溶液(浓度0.5M)，40℃下反应1小时，然后加入丁二烯，继续反应1小时，最后再加入第三段的4-乙烯苄基乙酸酯和苯乙烯混合单体，再反应1小时。反应结束后，将聚合液体压入加氢釜，通入氢气终止反应。半小时后，加入1mL浓度为0.02mol/L邻甲基苯甲酸甲酯，30mg催化剂二氯二茂钛，再通入氢气，控制温度70℃、压力2MPa，反应结束6小时后出料。
表1 实施例1中混合单体的摩尔配比
Figure PCTCN2018093648-appb-000003
如图1所示，向(1)产物混合液中，加入10ml浓度为50wt％氢氧化钠碱水溶液，碱水溶液中含5wt％四丁基溴化铵，于60℃水解3小时，最后向反应液中加入甲醇，使产物沉淀，并烘干，即得到带羟基的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。其合成配方和 工艺以及分子量测试结果见表2，红外光谱见图2， 1H NMR见图4。
表2 带羟基的苯乙烯-乙烯/丁烯-苯乙烯线性嵌段共聚物的合成配方
Figure PCTCN2018093648-appb-000004
(2)制备含呋喃基的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物
将5g羟基苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物溶于氯仿中得到质量浓度10％的溶液，按表3所示配比加入呋喃酰氯，4-二甲氨基吡啶(DAMP)，缓慢加入吡啶，用量为呋喃酰氯摩尔量的1.5倍，室温反应6小时后，加入乙醇使产物沉淀出来，过滤干燥，即得含呋喃基的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，其红外光谱见图3，1H NMR测试结果见图5。
(3)制备含可逆交联键的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料
向所得呋喃基的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物加入N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺，0.003mmol 2-叔丁基对苯二酚，在二甲苯溶剂中于100℃反应15小时，脱去溶剂，得到耐溶剂的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，性能如表3。
表3 含可逆交联键的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料的合成配方及性能
Figure PCTCN2018093648-appb-000005
由以上结果可知，本发明通过调节单体中羟基的含量，可以制备出不同羟基含量的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，进而制备出不同呋喃基含量的苯乙烯类共聚物。含呋喃基的苯乙烯类共聚物与N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺交联制备的交联苯乙烯共聚物很好的改善了聚苯乙烯共聚物的耐溶剂性能，其中样品1-1、1-2交联后耐溶剂性能更优。
如图6(1)为带羟基的苯乙烯类共聚物(样品1-2)在甲苯中的溶解性能测试结果。结果表明甲苯可以溶解带羟基的苯乙烯类共聚物。将带呋喃基的苯乙烯类共聚物与N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺在100℃下反应生成含可逆交联键的苯乙烯类共聚物材料，将所得材料置于甲苯溶剂中，常温下24h后材料仅仅是轻微溶胀，并未溶解，如图6(2)和图7左下图所示，表明带呋喃基的苯乙烯类共聚物交联后耐溶剂性能大幅度提高，可以用于电线电缆包覆绝缘材料、自行车实心轮胎等将上述交联后的苯乙烯类共聚物材料在140℃加热4h，其交联键发生断裂，可以在甲苯中形成均一的溶液(如图7右下图)，因而该材料可进行二次加工。
实施例2
(1)阴离子聚合制备含羟基的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物
按表1中1-4、1-5、1-6和1-7的配方，合成含4-乙烯苄基乙酸酯结构单元的线性苯乙烯-丁二烯-苯乙烯线性嵌段共聚物，在加入第三段反应单体并反应1小时后，将物料压入加氢釜，按表4配方，加入偶联剂，40℃继续反应30min，得到含4-乙烯苄基乙酸酯结构单元的星型苯乙烯-丁二烯-苯乙烯嵌段共聚物胶液。
反应结束后按照实施例1的方法氢化处理，沉淀出产物并烘干，得到4-乙烯苄基乙酸酯结构单元的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物胶液。
将产物溶于正辛烷中形成溶液，加入50ml浓度为40wt％氢氧化钠碱水溶液，含5wt％十六烷基三甲基溴化铵，于70℃水解1小时，再将反应液缓慢注入100℃浓度为10％氢氧化钠沸水中煮胶，脱除溶剂和其他杂质，沉淀出产物，烘干，即得到羟基化的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
表4 含羟基的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物的合成配方及分子量测试结果
Figure PCTCN2018093648-appb-000006
(2)合成含呋喃基的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物
将5g羟基化的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物溶于氯仿中得到质量浓度10％的溶液，按表5所示配方加入2-呋喃甲酸，4-二甲氨基吡啶(DAMP)，二环己基碳二亚胺(DCC)，80℃反应6小时后，加入乙醇使产物沉淀出来，过滤干燥，即得含呋喃基的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物。
表5 含可逆交联键的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料的合成配方及性能
Figure PCTCN2018093648-appb-000007
(3)制备含可逆交联键的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料
向所得含呋喃基的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物中加入N,N'-(1,4-亚苯基)双马来酰亚胺，0.004mmol甲基氢醌，于170℃开炼120min，得到耐溶剂的星型苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料。
实施例3
(1)阴离子聚合制备带羟基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物
将1L聚合釜抽真空，用高纯氮气置换三次，先加入650ml纯化的环己烷，设计固含量15％，再按表6和表7配方加料。先加入第一段的对4-乙酰氧基苯乙烯和苯乙烯混合单体、1g四氢糠醇乙基醚，开搅拌，再加入叔丁基锂溶液(浓度0.5M)，60℃下反应50min，然后升温至70℃加入异戊二烯，继续反应1小时，最后再加入第三段的对4-乙酰氧基苯乙烯和苯乙烯混合单体，再反应1小时。反应结束后，将聚合液体压入加氢釜，通入氢气终止反应。半小时后，30mg催化剂(环烷酸镍/三异丁基铝，n(A)l:n(Ni)＝5:1)，再通入氢气，控制温度50℃、压力0.5MPa，反应结束后出料、沉淀、过滤。
表6 实施例2中混合单体的摩尔配比
Figure PCTCN2018093648-appb-000008
将产物溶于正庚烷或正己烷，加入50ml浓度为30wt％氢氧化钠碱水溶液，碱水中含15wt％四丁基溴化铵，于60℃水解3小时，最后向反应液中加入甲醇，使产物沉淀，并烘干，即得到带羟基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物。其合成配方和工艺以及分子量测试结果见表7。
表7 带羟基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物的合成配方及分子量测试结果
Figure PCTCN2018093648-appb-000009
(2)制备含呋喃基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物
在搅拌下，将呋喃甲醇缓慢滴加到甲苯二异氰酸酯中，控制呋喃甲醇和异氰酸酯用量为1.1:1，按呋喃甲醇摩尔用量的0.1％加入二月桂酸二丁基锡，50℃反应2小时，得到端基为异氰酸酯基的呋喃。再将含5g带羟基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物的四氢呋喃溶液(质量浓度30％)滴加到端基为异氰酸酯基的呋喃中(端基为异氰酸酯基的呋喃用量见表8)，50℃下继续反应2小时，加入蒸馏水，使产物沉淀出来，过滤干燥，即得到含呋喃基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物。
(3)制备含可逆交联键的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物材料
向所得呋喃基的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物加入1,2-双(马来酰亚胺基乙氧基)乙烷，0.002mmol四甲基哌啶氮氧化物，在甲苯溶剂中于100℃反应15小时，加入甲醇沉淀并烘干，得到耐溶剂的含可逆交联键的苯乙烯-乙烯/丙烯-苯乙烯嵌段共聚物材料，性能如表8。
表8 含可逆交联键的苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物材料的合成配方及性能
Figure PCTCN2018093648-appb-000010
由以上结果可知，本发明制备的含呋喃基的苯乙烯类共聚物与1,2-双(马来酰亚胺基乙氧基)乙烷交联制备的交联苯乙烯共聚物溶胀度较低，很好的改善了聚苯乙烯共聚物的耐溶剂性能。
实施例4
(1)阴离子聚合制备带羟基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物
向500ml烧瓶中加入100ml氯仿，0.1mol 4-乙烯基苯基甲醇，0.1mol环戊基甲酰氯，0.6g 4-二甲氨基吡啶，8g吡啶，20℃下反应12小时。反应结束后加入蒸馏水，待分层，取有机层反复用蒸馏水洗涤5次，最后50℃下减压蒸馏，去除氯仿和水，得到对4-乙烯苄基环戊基甲酸酯。
将1L聚合釜抽真空，用高纯氮气置换三次，先加入650ml纯化的环己烷，设计固含量10％。依次加入对11.6g 4-乙烯苄基环戊基甲酸酯(占单体摩尔含量7.1％)、4.17g苯乙烯、1.2gα-甲基苯乙烯、0.59mol丁二烯、0.234mmol N,N-二甲基四氢糠胺，开搅拌，再加入2.08ml仲丁基锂溶液(浓度0.5M)，60℃下反应2小时，最后将反应液压入终止釜中，加入乙醇终止反应。
向产物混合液中，加入15ml浓度为40wt％氢氧化钠碱水溶液，碱水中含5wt％十 二烷基三甲基溴化铵，于80℃水解2小时，最后向反应液中加入甲醇，使产物沉淀，并烘干，即得到带羟基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物，数均分子量约4.8万，分子量分布宽度1.17，含羟基的结构单元占比例15.4％。
(2)制备含呋喃基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物
将糠胺缓慢滴加到二苯基甲烷二异氰酸酯中，按糠胺摩尔量的0.5％加入二月桂酸二丁基锡，控制糠胺和异氰酸酯用量为1.05:1，40℃反应2小时，得到端异氰酸酯基呋喃3.1g。再将含5g羟基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物的四氢呋喃溶液(质量浓度20％)滴加到端异氰酸酯基呋喃中，50℃反应2小时，加入蒸馏水，使产物沉淀出来，过滤干燥，即得到含呋喃基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物。
(3)制备含可逆交联键的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物材料
向所得呋喃基的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚物加入4.95mmol N,N'-间苯撑双马来酰亚胺，0.005mmol四甲基哌啶氮氧化物，于120℃甲苯反应10小时，得到耐溶剂的苯乙烯-α-甲基苯乙烯-丁二烯无规共聚材料，溶胀度4.5，凝胶含量81％，拉伸强度22.3MPa。
实施例5
(1)阴离子聚合方法制备带羟基的苯乙烯-异戊二烯无规共聚物
向500ml烧瓶中加入100ml氯仿，6.71g 4-乙烯基苯基甲醇，8.43g 3-苯基丙酰氯，0.6g 4-二甲氨基吡啶，9g三乙胺，25℃下反应9小时。反应结束后加入蒸馏水，待分层，取有有机层反复用蒸馏水洗涤5次，最后50℃下减压蒸馏，去除氯仿和水，得到对4-乙烯苄基(3-苯基)丙酸酯。
将1L聚合釜抽真空，用高纯氮气置换三次，先加入650ml纯化的环己烷，设计固含量10％。依次加入对13.31g对4-乙烯苄基(3-苯基)丙酸酯(占单体摩尔含量9.0％)、5.2g苯乙烯、31g异戊二烯、0.30mmol二甲基甲酰胺，开搅拌，再加入1.66ml正丁基锂溶液(浓度0.5M)，40℃下反应3小时，最后将反应液压入终止釜中，加入乙醇终止反应。
向产物混合液中，加入15ml浓度为36wt％氢氧化钠碱水溶液，碱水中含8wt％苄基三乙基溴化铵，于45℃水解10小时，最后向反应液中加入甲醇，使产物沉淀，并烘干，即得到带羟基的苯乙烯-异戊二烯无规共聚物，数均分子量约5.9万，分子量分布宽度1.12，含羟基的结构单元占比例15.64wt％。
(2)制备含呋喃基的苯乙烯-异戊二烯无规共聚物
将5g羟基的苯乙烯-异戊二烯无规共聚物溶于二氯乙烷中，控制质量浓度15％，加入14.5mol呋喃酰氯，1mmol 4-二甲氨基吡啶(DAMP)，缓慢加入0.09mol吡啶，室温反应8小时后，加入乙醇使产物沉淀出来，过滤干燥，即得含呋喃基的苯乙烯-异戊二烯无规共聚物。
(3)制备含可逆交联键的苯乙烯-异戊二烯无规共聚物材料
向所得呋喃基的苯乙烯-异戊二烯无规共聚物加入5mmol N,N'-间苯撑双马来酰亚胺，0.01mmol四甲基哌啶氮氧化物，于120℃甲苯反应10小时，加入甲醇沉淀并烘干，得到耐溶剂的苯乙烯-异戊二烯无规共聚物，溶胀度3.8，凝胶含量78％，拉伸强度24.3MPa。
实施例6
(1)阳离子聚合方法制备带羟基的苯乙烯-异丁烯无规共聚物
控制固含量8％，向1L聚合釜中依次加入500g一氯甲烷(预冷至-60℃)、7.81g苯乙烯、4.4g对4-乙烯苄基乙酸酯(占单体摩尔含量4.2％)、27.8g异丁烯，开搅拌混合均匀，并降温至-80℃左右。开始向反应釜中缓慢滴加20ml含12.8mmol/L二氯乙基铝的正己烷溶液，并维持聚合温度。滴加完成后继续反应15分钟，然后加入2ml预冷过的含有0.125mol/L氢氧化钠的乙醇溶液终止聚合，除去反应溶剂并水洗、干燥，得到含4-乙烯苄基乙酸酯结构单元的苯乙烯-异丁烯无规共聚物。
将产物溶于1L甲苯中，加入30ml浓度为45wt％氢氧化钾碱水溶液，碱水中含5wt％四丁基氯化铵，于50℃水解8小时，最后向反应液中加入甲醇，使产物沉淀、水洗，并烘干，即得到带羟基的苯乙烯-异丁烯无规共聚物，分子量16.2万，分子量分布宽度5.6，含羟基的结构单元占比例8.6wt％。
(2)制备含呋喃基的苯乙烯-异丁烯无规共聚物
将5g羟基的苯乙烯-异丁烯无规共聚物溶于氯仿中，按实施例5的方法合成含呋喃基的苯乙烯-异丁烯无规共聚物，呋喃甲酰氯用量为9mmol，DAMP用量不变，缓慢加入0.045mol吡啶。
(3)制备含可逆交联键的苯乙烯-异丁烯无规共聚物材料
向所得呋喃基的苯乙烯-异丁烯无规共聚物加入3.6mmol N,N'-间苯撑双马来酰亚胺，0.002mmol甲基氢醌，于120℃甲苯中反应10小时，加入甲醇沉淀并烘干，得到耐溶剂的苯乙烯-异丁烯无规共聚物，溶胀度6.9，凝胶含量68％，拉伸强度21.3MPa。
实施例7
(1)阳离子聚合方法制备带羟基的苯乙烯-异戊二烯无规共聚物
控制固含量为8％，按照实施例6步骤1的方法，反应溶剂为正己烷、7.81g苯乙烯、4.4g对4-乙烯苄基乙酸酯(占单体摩尔含量4.2％)、27.8g异戊二烯，反应温度为-30℃、引发剂为5.5ml 50mmol/L四氯化钛的二氯甲烷溶液，反应时间45分钟，其他条件相同，再水解，得到带羟基的苯乙烯-异戊二烯无规共聚物，分子量15.9万，分子量分布宽度6.2，含羟基的结构单元占比例8.6wt％。
(2)制备含呋喃基的苯乙烯-异丁烯无规共聚物
将5g羟基的苯乙烯-异戊二烯无规共聚物溶于环己烷中，按实施例5的方法合成含呋喃基的苯乙烯-异戊二烯无规共聚物，呋喃甲酰氯摩尔用量为9mmol，DAMP用量不变，缓慢加入0.045mol吡啶。
(3)制备含可逆交联键的苯乙烯-异戊二烯无规共聚物材料
向所得5g呋喃基的苯乙烯-异戊二烯无规共聚物加入1.62mmol 1,2-二(马来酰亚胺)乙烷，0.001mmol甲基氢醌，于140℃氯仿反应6小时，冷却并加入乙醇沉淀，过滤并烘干，得到耐溶剂的苯乙烯-异戊二烯无规共聚物，溶胀度24.1，凝胶含量52.2％，拉伸强度12.6MPa。
实施例8
(1)阳离子聚合方法制备带羟基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物
控制固含量10％，向1L聚合釜中依次加入500g一氯甲烷(预冷至-80℃)、15g对4-乙烯苄基乙酸酯(占单体摩尔含量12％)、35g摩尔比为20:1的异丁烯/3甲基-1-丁烯混合物，开搅拌混合均匀，并降温至-100℃左右。开始向反应釜中缓慢滴加11ml含19.5mmol/L三氯化铝的二氯甲烷溶液，并维持聚合温度。滴加完成后继续反应12分钟，然后加入3ml预冷过的含有0.125mol/L氢氧化钠的甲醇溶液终止聚合，除去反应溶剂并水洗、干燥，得到含4-乙烯苄基乙酸酯-异丁烯-3-甲基-1-丁烯无规共聚物。
将产物溶于1L二甲苯中，加入40ml浓度为25wt％氢氧化钾碱水溶液，碱水中含5wt％十四烷基三甲基溴化铵，于35℃水解12小时，最后向反应液中加入甲醇，使产物沉淀、水洗，并烘干，即得到带羟基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物，分子量26.6万，分子量分布宽度4.5，含羟基的结构单元占比例24wt％。
(2)制备含呋喃基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物
将5g带羟基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物溶于氯仿中，按实施例2样品2-1的方法合成含呋喃基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物，呋喃甲酸摩尔用量为22mmol，DMAP和DCC用量相同。
(3)制备含可逆交联键的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物材料
向所得呋喃基的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物加入5.6mmol 1,6-二(马来酰亚胺基)己烷，0.003mmol 2-叔丁基对苯二酚，于80℃二氯甲烷中回流反应23小时，再升温至140℃反应1小时，加入甲醇沉淀并烘干，得到耐溶剂的苯乙烯-异丁烯-3-甲基-1-丁烯无规共聚物，溶胀度4.1，凝胶含量78％，拉伸强度15.3MPa。
实施例9
(1)阳离子聚合方法制备带羟基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物
控制固含量15％，向1L聚合釜中依次加入500g二氯甲烷(预冷至-90℃)、8.1g对4-乙酰氧基苯乙烯(占单体摩尔含量4.3％)、6.9g苯乙烯、60g摩尔比为15:1异丁烯/4-甲基-1-戊烯混合物，开搅拌混合均匀，并降温至-110℃左右。开始向反应釜中缓慢滴加30ml含21.3mmol/L一氯二乙基铝的正己烷溶液，并维持聚合温度。滴加完成后继续反应20分钟，然后加入3ml预冷过的含有0.2mol/L氢氧化钾的甲醇溶液终止聚合，除去反应溶剂并水洗、干燥，得到含对4-乙酰氧基苯乙烯结构单元的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物。
将产物溶于1L环己烷中，加入30ml浓度为30wt％氢氧化钠碱水溶液，碱水中含5 wt％三辛基甲基溴化铵，于45℃水解9小时，最后向反应液中加入乙醇，使产物沉淀、水洗，并烘干，即得到带羟基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物，分子量11.8万，分子量分布宽度4.3，含羟基的结构单元的比例8.2wt％。
(2)合成含呋喃基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物
将5g带羟基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物溶于四氢呋喃中，按实施例3中样品3-5所采用方法和配方合成含呋喃基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物。
(3)制备含可逆交联键的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物材料
向所得呋喃基的苯乙烯-异丁烯-4-甲基-1-戊烯无规共聚物加入2.1mmol 1,2-双(马来酰亚胺基乙氧基)乙烷，0.001mmol 2,5-二叔丁基对苯二酚，于80℃四氢呋喃回流反应22小时，再升温至120℃反应2小时，加入甲醇沉淀并烘干，得到耐溶剂的苯乙烯-异丁烯无规共聚物，溶胀度5.2，凝胶含量64.2％，拉伸强度16.7MPa。
实施例10
(1)阳离子聚合方法制备带羟基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物
控制固含量15％，向1L聚合釜中依次加入500g二氯乙烷(预冷至-20℃)、9.8g对4-乙酰氧基苯乙烯(占单体摩尔含量4.3％)、5.2g苯乙烯、60g摩尔比为15:1异丁烯/1,3-戊二烯混合物，开搅拌混合均匀。向反应釜中注入18.75ml含20mmol/L四氯化锡的二氯甲烷溶液，并维持聚合温度继续反应1小时，然后加入3ml预冷过的含有0.2mol/L氢氧化钾的甲醇溶液终止聚合，除去反应溶剂并水洗、干燥，得到含对4-乙酰氧基苯乙烯结构单元的苯乙烯-异丁烯-1,3-戊二烯无规共聚物。
将产物溶于1L环己烷中，加入20ml浓度为50wt％氢氧化钠碱水溶液，碱水中含5wt％四丁基溴化铵，于30℃水解12小时，将反应液倒入沸水中，沉淀出产物，烘干后即得到带羟基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物，分子量29.2万，分子量分布宽度3.8，含羟基的结构单元的比例10.02wt％。
(2)合成含呋喃基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物
将5g带羟基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物溶于二氯甲烷中，按实施例3中样品3-4所采用的方法和配方合成含呋喃基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物。
(3)制备含可逆交联键的苯乙烯-异丁烯-1,3-戊二烯无规共聚物材料
向40g呋喃基的苯乙烯-异丁烯-1,3-戊二烯无规共聚物加入21mmol 1,4-双(马来酰亚胺基)丁烷，0.42mmol对甲氧基苯酚，于240℃密炼15分钟，得到耐溶剂的苯乙烯-异丁烯无规共聚物，溶胀度15.2，凝胶含量58.9％，拉伸强度14.5MPa。
本发明对实施例1中样品1-2所得的含可逆交联键的苯乙烯类共聚物材料进行了耐溶剂性(图6)和解聚试验(图7)。带羟基的苯乙烯类共聚物(样品1-2)在常温下，很快溶解于甲苯中，如图6(1)所示。呋喃基苯乙烯类共聚物与N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺在100℃下反应生成含可逆交联键的苯乙烯类共聚物材料，将所得材料置于甲苯溶液中，常温下放置24h后，材料仍不能溶解在甲苯中，如图6(2)和图7左下图所 示，表明呋喃基的苯乙烯类共聚物发生了交联，表现出良好的耐溶剂性；当在140℃下加热4h后，材料能完全溶解在甲苯中(图7右下图)，说明在高温下，可逆交联键发生了断裂，重新形成了带呋喃基的苯乙烯类共聚物和马来酰亚胺，因而能进行再次加工。
本发明采用带呋喃基的活性单体与带羟基的苯乙烯类共聚物直接或间接反应，制备出带呋喃基的苯乙烯类共聚物。本发明制备的带呋喃基的苯乙烯类共聚物可以与马来酰亚胺反应制备含可逆交联键的共聚物材料，该共聚物材料表现良好的耐溶剂性，且具有二次加工能力，有望应用于可回收的电线电缆包覆材料、自行车轮胎等领域，极具工业应用价值。此外，该呋喃基的苯乙烯类共聚物上的呋喃基结构单元比例可以通过特定聚合工艺来加以控制，从而改变可逆交联共聚物材料的交联度，满足不同的应用领域的需求。

Claims (24)

  1. 一种苯乙烯类交联共聚物的制备方法，其特征在于：带呋喃基的苯乙烯类共聚物与多官能度马来酰亚胺衍生物通过溶液聚合或熔融聚合制得；
    所述的溶液聚合为：将带呋喃基的苯乙烯类共聚物溶于有机溶剂中制备浓度不超过30wt％的共聚物溶液，再加入阻聚剂、多官能度马来酰亚胺衍生物，在80～140℃反应6～24h，沉淀出产物，烘干即得；
    所述的熔融聚合为：向带呋喃基的苯乙烯类共聚物中依次加入阻聚剂、多官能度马来酰亚胺衍生物，于170～240℃下混炼15～120分钟，冷却即得；
    其中，带呋喃基的苯乙烯类共聚物和双马来酰亚胺衍生物的用量为能使马来酰亚胺基完全反应的量；
    所述的带呋喃基的苯乙烯类共聚物制备方法为：将带羟基的苯乙烯类共聚物溶解到有机溶剂中得到带羟基的苯乙烯类共聚物的溶液，依次加入催化剂、含呋喃基的活性单体，20～50℃反应2～6h，反应结束后，用水和/或醇沉淀出产物，烘干即得；
    其中，所述含呋喃基的活性单体是能与羟基直接或间接反应的呋喃衍生物中的任意一种；含呋喃基的活性单体与含羟基的苯乙烯类共聚物中羟基的摩尔比为0.5～3:1；
    所述催化剂为吡啶、吡啶衍生物、叔胺、碳二亚胺衍生物、有机锡化合物中的任意一种或多种，催化剂与带呋喃基的活性单体的摩尔量比0.001～5:1；
    所述带羟基的苯乙烯类共聚物数均分子量为0.1万～50万。
  2. 根据权利要求1所述的制备方法，其特征在于：所述带羟基的苯乙烯类共聚物数均分子量为5万～50万。
  3. 根据权利要求1所述的制备方法，其特征在于：所述带羟基的苯乙烯类共聚物中羟基结构单元占共聚物中所有结构单元的质量分数P为0<P≤33％，优选为3≤P≤25％；和/或，所述带羟基的苯乙烯类共聚物的溶液的质量浓度不超过30％；和/或，所述带呋喃基的活性单体为呋喃甲酰氯、呋喃甲酸、糠醇、糠胺中的任意一种；和/或，所述含呋喃基的活性单体与含羟基的苯乙烯类共聚物中羟基单元的摩尔比为1～2:1。
  4. 根据权利要求3所述的制备方法，其特征在于：所述带羟基的苯乙烯类共聚物溶液的浓度为10～30wt％。
  5. 根据权利要求1所述的制备方法，其特征在于：所述带呋喃基的苯乙烯类共聚物数均分子量M n为0.1万<M n<120万；优选地，所述带呋喃基的苯乙烯类共聚物数均分子量M n为5万≤M n≤85万。
  6. 根据权利要求1所述的制备方法，其特征在于：所述带呋喃基的苯乙烯衍生物结构单元占共聚物中所有结构单元的质量分数N为0<N≤75％，优选地，5％≤N≤55％。
  7. 根据权利要求1所述的制备方法，其特征在于：所述带呋喃基的苯乙烯类共聚物的制备方法中，有机溶剂选自烷烃、卤代烃、醚、芳香烃溶剂中的任意一种，优选地，所 述的有机溶剂选自环己烷、二氯甲烷、二氯乙烷、三氯甲烷、四氢呋喃、甲苯中的任意一种。
  8. 根据权利要求1所述的制备方法，其特征在于：所述的多官能度马来酰亚胺衍生物中含有2个或2个以上的马来酰亚胺官能团，优选为N,N'-(4,4'-亚甲基二苯基)双马来酰亚胺、N,N'-(1,4-亚苯基)双马来酰亚胺、1,2-双(马来酰亚胺基乙氧基)乙烷、N,N'-间苯撑双马来酰亚胺、1,2-二(马来酰亚胺)乙烷、1,4-双(马来酰亚胺基)丁烷、1,6-二(马来酰亚胺基)己烷。
  9. 根据权利要求1所述的制备方法，其特征在于：所述的多官能度马来酰亚胺衍生物中马来酰亚胺基与带呋喃基的苯乙烯类共聚物中呋喃基的摩尔比为0.1～1:1。
  10. 根据权利要求1所述的制备方法，其特征在于：所述溶液聚合过程中，有机溶剂为能同时溶解带呋喃基的苯乙烯类共聚物和多官能度马来酰亚胺衍生物的溶剂，优选为甲苯、二甲苯、四氢呋喃、二氯甲烷、三氯甲烷；和/或，所述的带呋喃基的苯乙烯类共聚物溶液的质量浓度为10～20％。
  11. 根据权利要求1所述的制备方法，其特征在于：所述的阻聚剂为酚类化合物、醌类化合物、氮氧化合物中的一种或多种；和/或，所述阻聚剂与多官能度马来酰亚胺衍生物的摩尔比为0～2:100。
  12. 根据权利要求1所述的制备方法，其特征在于：所述带羟基的苯乙烯类共聚物的制备方法包括以下步骤：
    (1)含有式I和/或式II结构的单体与其他乙烯基单体通过阴离子聚合或阳离子聚合制备共聚物；
    (2)将步骤(1)所得共聚物溶解到溶剂中形成共聚物溶液，再与碱水混合，于30～100℃下水解1～12h，沉淀出共聚物，烘干后即得带羟基的苯乙烯类共聚物；
    Figure PCTCN2018093648-appb-100001
    其中，R 1、R 2分别独立地选自C 1～12烷基、C 1～12环烷基、C 6～12芳基、C 1～12杂环芳基、C 1～12杂环烷基，其中所述烷基、环烷基、芳基、杂环芳基、杂环烷基可以进一步被1～4个独立选自C 1～6烷基、C 1～6环烷基、C 1～6烷氧基、C 1～6烷胺基、C 1～6烷酯基、C 1～6烷酰基的取代基取代；
    所述的其他乙烯基单体为能与苯乙烯单体进行阴离子或阳离子聚合的烯烃单体中的一种或多种；
    所述的阴离子聚合包括以下步骤：用分步加料或一次性加料方式，将具有式I和/或 式II所示结构的单体和其他乙烯基单体加入到含有活化剂、溶剂的体系中混合均匀，再加入引发剂于25～90℃下聚合30～180分钟，反应终止后进行氢化或不氢化，最后脱除溶剂，得到含有式I和/或式II结构单元的共聚物；
    其中，阴离子聚合中所述的活化剂为含氧和/或含氮的但不含活性氢的极性化合物，溶剂为任何能同时溶解单体的溶剂，引发剂为烷基金属化合物、烷氧基金属化合物中的任意一种；
    所述的阳离子聚合包括以下步骤：用分步加料或一次性加料方式，将具有式I和/或式II所示结构的单体和其他乙烯基单体加入卤代烃和/或烷烃溶剂中混合均匀，降低温度至0℃以下，再加入Lewis酸引发剂，聚合时间不超过1小时，反应终止后进行氢化或不氢化，最后得到含有式I和/或式II结构单元的共聚物。
  13. 根据权利要求12所述的制备方法，其特征在于：所述R 1、R 2分别独立地选自C 1～8烷基、C 1～8环烷基、C 6～8芳基、C 1～8杂环芳基、C 1～8杂环烷基；优选地，所述R 1、R 2分别独立地选自甲基、乙基、丙基、异丙基。
  14. 根据权利要求12所述的制备方法，其特征在于：所述其他乙烯基单体为苯乙烯、α-甲基苯乙烯、异丁烯、3-甲基-1-丁烯、4-甲基-1-戊烯、丁二烯、1,3-戊二烯、异戊二烯中的一种或多种。
  15. 根据权利要求12-14所述的制备方法，其特征在于：步骤(1)中，所述具有式I和/或式II所示结构的单体的质量分数N为0<N≤33％，优选为3≤N≤25％。
  16. 根据权利要求12所述的制备方法，其特征在于：所述阴离子聚合中，反应体系中单体的质量浓度不超过15％；和/或，在设计分子量下，引发剂摩尔用量为理论用量的1～1.25倍；和/或，引发剂与活化剂的摩尔比为1:0.02～20，优选为1:0.07～17。
  17. 根据权利要求12或16所述的制备方法，其特征在于：所述阴离子聚合中，活化剂为四氢呋喃、二氧六环、四氢糠醇乙基醚、N,N-二甲基四氢糠胺、二甲基甲酰胺中的一种或多种；和/或，溶剂为环己烷；和/或，引发剂为正丁基锂、仲丁基锂、叔丁基锂中的任意一种。
  18. 根据权利要求12所述的制备方法，其特征在于：所述阳离子聚合中，反应体系中单体的质量浓度不超过15％；和/或，在设计分子量下，所述引发剂摩尔用量为理论用量的1-1.5倍。
  19. 根据权利要求12或18所述的制备方法，其特征在于：所述阳离子聚合中，溶剂为一氯甲烷、二氯甲烷、二氯乙烷、正己烷中的一种或多种；和/或，引发剂为三氯化铝、二氯乙基铝、一氯二乙基铝、三乙基铝、四氯化锡、四氯化钛中任意一种。
  20. 根据权利要求12所述的制备方法，其特征在于：步骤(2)中，所述共聚物溶液质量浓度不超过15％；和/或，所述溶剂为任何能溶解含有式I和/或式II结构单元的共聚物且不与碱水反应的溶剂；和/或，共聚物溶液与碱水的质量比为100～20:1；和/或，所述的碱水溶液由碱金属氢氧化物、相转移催化剂和水组成；碱金属氢氧化物的质量浓度ω 的范围为0<ω≤55％；相转移催化剂的质量浓度δ的范围为0<δ≤15％。
  21. 根据权利要求20所述的制备方法，其特征在于：步骤(2)中，所述溶剂为环己烷、正己烷、正庚烷、正辛烷、甲苯、二甲苯中的任意一种；和/或，所述碱金属氢氧化物为氢氧化锂、氢氧化钾、氢氧化钠中的任意一种，且质量浓度ω的范围为25≤ω≤50％；和/或，所述相转移催化剂为季铵盐、烷基卤化铵、叔胺类、季铵碱类、季膦盐类、环状冠醚类中的任意一种，且在碱水中的质量浓度δ的范围为5≤δ≤15％；优选地，相转移催化剂为烷基卤化铵类。
  22. 一种苯乙烯类交联共聚物，其特征在于：分子中含有呋喃基与马来酰亚胺基双烯加成得到的可逆交联键，苯乙烯类交联共聚物在甲苯中的溶胀度为3.8～34.2。
  23. 根据权利要求22所述的苯乙烯类交联共聚物，其特征在于：它是以权利要求1～21任一项所述制备方法制备而得。
  24. 一种权利要求22或23所述苯乙烯类交联共聚物的用途，其特征在于：可用于制备耐溶剂且能反复成型加工的电线电缆料、轮胎。
PCT/CN2018/093648 2017-08-02 2018-06-29 带可逆交联键的苯乙烯类共聚物及其制备方法 WO2019024633A1 (zh)

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