CN112608402B

CN112608402B - Styrene block copolymer and preparation method thereof

Info

Publication number: CN112608402B
Application number: CN202011435277.9A
Authority: CN
Inventors: 吴一弦; 魏志涛; 张航天
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2020-12-10
Filing date: 2020-12-10
Publication date: 2022-02-11
Anticipated expiration: 2040-12-10
Also published as: CN112608402A

Abstract

The invention belongs to the field of elastomers, and discloses a styrene block copolymer and a preparation method thereof. The preparation method of the styrene block copolymer comprises the following steps: s1, carrying out sequential active cationic copolymerization on isobutene, styrene and p-methylstyrene in the presence of a cationic initiator to obtain a block copolymer; s2, carrying out bromination/chlorination reaction on the block copolymer and a bromination/chlorination reagent to obtain a brominated/chlorinated block copolymer; s3, subjecting the brominated/chlorinated block copolymer to pendant azonium/phosphonium ion functionalization, amine group functionalization, or hydroxyl group functionalization. The styrene block copolymer provided by the invention has the advantages that the styrene block copolymer side group functional groups interact with each other to form a thermal reversible physical crosslinking point and a three-dimensional network structure, so that the material has excellent self-repairing performance at a certain temperature, the use temperature, the thermal stability and the hydrophilicity of the material are improved, the mechanical property is improved, and the material is reinforced and toughened.

Description

Styrene block copolymer and preparation method thereof

Technical Field

The invention belongs to the field of elastomers, and particularly relates to a styrene block copolymer and a preparation method thereof.

Background

Thermoplastic elastomers (TPEs) are elastomers having rubber elasticity at normal temperature and moldable at high temperature. The thermoplastic elastomer has the structural characteristics that different resin segments and rubber segments are formed by chemical bonds, the resin segments form physical cross-linking points by virtue of inter-chain acting force, and the rubber segments are high-elasticity segments and contribute to elasticity. Therefore, the thermoplastic elastomer has the physical and mechanical properties of vulcanized rubber and the processing properties of thermoplastic plastics, and is widely applied to the fields of electric wires and cables, automobile manufacturing, household appliances, medical appliances and the like. Thermoplastic elastomers are widely used, and classified into polyurethanes, polyesters, polyamides, polyolefins, silicones, organofluorine, acrylates, polyvinyl chloride, styrene block copolymers, and the like according to their chemical compositions. Among them, the styrenic block copolymer thermoplastic elastomer accounts for the largest proportion and is most widely used, see: liuliu plexus, Wuhui wool, Zhang Grou, research progress on thermoplastic elastomers, Chinese rubber, 2009,36(8): 17-21. Styrenic block copolymer thermoplastic elastomers mainly include polystyrene-b-poly (ethylene-co-butylene) -b-polystyrene (SEBS), polystyrene-b-polyisoprene-b-polystyrene (SIS), polystyrene-b-polybutadiene-b-polystyrene (SBS), polystyrene-b-poly (ethylene-co-propylene) -b-polystyrene (SEPS), poly (styrene-b-isobutylene-b-styrene) (SIBS).

The SIBS is a typical soft-segment fully saturated styrene block copolymer thermoplastic elastomer, has the characteristics of excellent air tightness, aging resistance, high electrical insulation, heat resistance, cold resistance, dielectric property and the like, and simultaneously has good damping performance, mechanical property and water/gas barrier property, see CN 1982350A. Since SIBS lacks polar functional groups, limiting its range of applications, its functional modification is one of the important technical solutions. In the prior art, isobutylene and p-vinylbenzyloxy-tert-butyl dimethylsilane or p-tert-dimethylsiloxy ethyl styrene are subjected to block copolymerization and then are hydrolyzed, and a hydroxyl group is introduced into a side group benzene ring of an SIBS block copolymer in a para-position to improve the polarity of the triblock polymer. See Laszlo spots, Abhijit Som, Rudolf dust, Controlled Deliever of Paclixel from Stem Coatings Using Poly (hydroxystyrene-b-isobutene-b-hydroxystyrene) and its acetyl derivative, Biomacromolecules,2005,6(5): 2570-; wu Y B, Li K, Xiao D, et al Surface Immobilization of Heparin on Functional polymeric-based Thermoplastic Elastomer as a Potential architectural Surface Science,2018,445. CN105669882A discloses a azonium ionized poly (styrene-b-isobutylene-b-styrene) block copolymer and a preparation method thereof, wherein SIBS is taken as a base material, and the copolymer is prepared through chloromethylation and azonium ionization in sequence, and does not contain a p-methylstyrene structural unit and a p-bromomethylstyrene structural unit. US20060292208a1 discloses a method for improving ion exchange capacity of a material by sulfonating and modifying a SIBS block copolymer and introducing sulfonate to the para position of a part of benzene rings in a polystyrene chain segment, see: elabd Y A, Napadesky E.Sulformation and catalysis of poly (styrene-isoprene-styrene) triblock copolymers at high ion-exchange capacities. Polymer,2004,45(9): 3037-3043.

In summary, in the prior art, functionalized SIBS is mainly prepared by copolymerization of isobutylene and a monomer with a complex structure and then hydrolysis, or by chloromethylation and sulfonation or azonium ionization of SIBS. However, the former monomer has a complex structure and a complicated preparation process, the monomer is a non-commercial product and needs to be specially synthesized and refined, and the step of obtaining the hydroxyl-functionalized polymer is also complicated; the latter sulfonation processes are often difficult to control and are prone to side reactions.

Disclosure of Invention

An object of the present invention is to provide a styrene-based block copolymer (FSMB) having a fully saturated polyisobutylene segment in the soft segment and a styrene-and p-methylstyrene-containing structural unit segment in the hard segment, which comprises a polyisobutylene segment having a structure represented by formula (1) and a random copolymerized segment of styrene and a substituted styrene structural unit having a structure represented by formula (2):

wherein n is 200-1800, the total number of m accounts for 0.5-29% of the total mole number of all the structural units, the total number of p accounts for 0.5-16% of the total mole number of all the structural units, the total number of q accounts for 0.05-10% of the total mole number of all the structural units, the total number of R accounts for 0.5-17% of the total mole number of all the structural units, a side group functional group X is chlorine or bromine, and a side group functional group R' is nitrogen-containing onium ions having a structure shown in a formula (3), phosphorus-containing onium ions having a structure shown in a formula (4), amino or hydroxyl;

wherein R is₁～R₇Each independently is H, C₁～C₂₀Alkyl or C₆～C₂₀Aryl of, X^-Is chloride ion or bromide ion.

The second purpose of the invention is to provide a preparation method of a styrene block copolymer, which comprises the following steps:

s1, carrying out sequential active cationic copolymerization on isobutene, styrene and p-methylstyrene in the presence of an initiating system to obtain a block copolymer of a polyisobutene chain segment with a structure shown in a formula (1) and a styrene and p-methylstyrene structural unit random copolymerization chain segment with a structure shown in a formula (5);

wherein n is 200-1800, the total number m of the styrene structural units accounts for 0.5-29% of the total mole number of all the structural units, and the total number g of the p-methylstyrene structural units accounts for 1.05-43% of the total mole number of all the structural units.

S2, carrying out bromination/chlorination reaction on the block copolymer obtained in the step S1 and a bromination/chlorination reagent in an organic solvent to obtain a brominated/chlorinated block copolymer;

s3, subjecting the brominated/chlorinated block copolymer obtained in step S2 to pendant azonium/phosphonium ion functionalization, amine group functionalization or hydroxyl group functionalization to obtain the styrenic block copolymer.

The functional groups of the side group of the styrene block copolymer comprise nitrogen onium ions, phosphorus onium ions, amino, hydroxyl and the like, wherein the soft section comprises a fully saturated polyisobutylene chain segment, the hard section comprises a styrene and p-methylstyrene structure unit chain segment, the functional groups of the side group of the styrene block copolymer interact to form a thermoreversible physical crosslinking point and a three-dimensional network structure, so that the material has self-repairing performance at a certain temperature, and the three-dimensional crosslinking network is favorable for improving the use temperature and the thermal stability of the material, improving the mechanical property and enhancing and toughening the material. In addition, the styrenic block copolymer has an increased hydrophilicity and an increased interaction with polar substances. The monomers of isobutene, styrene and p-methylstyrene used in the preparation process of the styrene block copolymer are all commercial products, the cost is low, the copolymerization activity of the p-methylstyrene is high, and the molecular weight, the random copolymerization structure and the composition of the obtained block copolymer can be regulated and controlled.

Detailed Description

The present invention will be described in detail below.

The styrene block copolymer provided by the invention consists of a polyisobutylene chain segment with a structure shown in a formula (1) and a random copolymerization chain segment of structural units of styrene and substituted styrene with a structure shown in a formula (2):

wherein n is 200-1800, preferably 250-1600, more preferably 300-1500; the total number of m accounts for 0.5-29% of the total mole number of all the structural units, preferably 0.7-27%, more preferably 0.8-25%; the total number of p accounts for 0.5-16% of the total mole number of all the structural units, preferably 0.8-14%, more preferably 1.0-12%; the total number of q accounts for 0.05-10% of the total mole number of all the structural units, preferably 0.08-9%, more preferably 0.1-8%; the total number of r accounts for 0.5-17% of the total mole number of all the structural units, preferably 0.7-15%, more preferably 0.8-13%; the pendant functional group X is chlorine or bromine, and the pendant functional group R' is a nitrogen-containing onium ion with a structure shown in a formula (3), a phosphorus-containing onium ion with a structure shown in a formula (4), an amine group or a hydroxyl group;

wherein R is₁～R₇Each independently is H, C₁～C₂₀Alkyl or C₆～C₂₀Preferably each independently is C₁～C₁₅Alkyl or C₆～C₁₅More preferably each independently is C₁～C₁₀Alkyl of (C)₆～C₁₀Phenyl or alkyl substituted phenyl of (a); x^-Is chloride ion or bromide ion.

In the styrene-based block copolymer provided by the invention, n, m, p, q and r represent the average number of each structural unit, wherein, each constitutional unit (structural units corresponding to m, p, q and r) in the random copolymerization chain segment of the styrene and the substituted styrene structural unit with the structure shown in the formula (2) is in a random copolymerization sequence.

The styrene block copolymer is a linear polymer or a star polymer;

when the styrene block copolymer is a linear polymer, the polyisobutylene chain segment shown in the formula (1) is connected with the random copolymerization chain segment of the styrene and substituted styrene structural units shown in the formula (2) through a chemical bond;

when the styrene block copolymer is a star polymer, the number of arms of the styrene block copolymer is 3-8, one end of a polyisobutylene chain segment shown in the formula (1) is chemically bonded to an initiator residue to be used as the center of the star polymer, and the other end of the polyisobutylene chain segment is chemically bonded with a random copolymerization chain segment of styrene and substituted styrene structural units shown in the formula (2).

The preparation method of the styrene block copolymer provided by the invention comprises the following steps:

s1, carrying out sequential active cationic copolymerization on isobutene, styrene and p-methylstyrene in the presence of an initiating system to obtain a block copolymer (SMB) of a polyisobutene chain segment with a structure shown in a formula (1) and a styrene and p-methylstyrene structural unit random copolymerization chain segment with a structure shown in a formula (5);

wherein n is 200-1800, the total number (m) of the styrene structural units accounts for 0.5-29% of the total mole number of all the structural units, and the total number (g) of the p-methylstyrene structural units accounts for 1.05-43% of the total mole number of all the structural units.

S2, carrying out bromination/chlorination reaction on the block copolymer obtained in the step S1 and a bromination/chlorination reagent in an organic solvent to obtain a brominated/chlorinated block copolymer (BSMB);

s3, subjecting the brominated/chlorinated block copolymer obtained in step S2 to pendant azonium ion functionalization, phosphonium ion functionalization, amine group functionalization or hydroxyl group Functionalization (FSMB).

In step S1, the sequential living cationic copolymerization reaction may be performed by using a monofunctional initiator/three-step polymerization reaction, or by using a bifunctional or polyfunctional initiator (e.g., 3 to 8 functional groups) or two-step polymerization reaction.

When a monofunctional initiator is used/three-step polymerization reaction, the method comprises the following steps:

s1-1, under the protection of nitrogen, styrene and p-methylstyrene are subjected to active cationic copolymerization in a reaction medium in the presence of an initiation system containing a monofunctional initiator and a co-initiator to obtain a poly (styrene-co-p-methylstyrene) active chain;

s1-2, adding isobutene into the reaction system of the step S1-1, and further initiating isobutene to perform living cationic polymerization reaction by the poly (styrene-co-p-methylstyrene) living chain obtained in the step S1-1 to obtain a poly (styrene-co-p-methylstyrene) -b-polyisobutylene two-block copolymer living chain;

s1-3, adding styrene and p-methylstyrene into the reaction system of the step S1-2, and further initiating the living cationic polymerization reaction of the styrene and the p-methylstyrene by the living chain of the diblock copolymer obtained in the step S1-2 to obtain the living chain of the poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene) triblock copolymer.

When a di-or multifunctional initiator/two-step polymerization reaction, the following steps are included:

s2-1, under the protection of nitrogen, carrying out active cationic polymerization reaction on isobutene in a reaction medium in the presence of an initiation system containing a bifunctional or polyfunctional initiator and a co-initiator to obtain a polyisobutene double-end or multi-end active chain;

s2-2, adding styrene and p-methylstyrene into the reaction system of the step S2-1, and further initiating the active cationic copolymerization reaction of the styrene and the p-methylstyrene by the polyisobutylene multi-terminal active chain obtained in the step S2-1 to obtain the linear poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene) triblock copolymer double-terminal active chain or star block copolymer multi-terminal active chain.

The monofunctional initiator may be at least one selected from the group consisting of water, protonic acid, phenol, tertiary alkyl (aryl) alcohol, tertiary alkyl (aryl) chloride, tertiary alkyl (aryl) ether, and tertiary alkyl (aryl) ester. Wherein the protonic acid is preferably selected from HCl and H₂SO₄And C₁-C₁₃At least one of the organic carboxylic acid compounds (3). Said C is₁-C₁₃Specific examples of the organic carboxylic acid compounds of (a) include, but are not limited to: formic acid, acetic acid, propionic acid, n-butyric acid, 3-dimethylbutyric acid, 2-dimethylbutyric acid, n-valeric acid, hexanvaleric acid, pivalic acid, 2-propylvaleric acid, 3-methylvaleric acid, n-hexanoic acid, isocaproic acid, cyclohexanoic acid, 2-ethylhexanoic acid, n-heptanoic acid, 2-propanoic acidAt least one of methylheptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, benzoic acid, phenylacetic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid. The phenol is preferably at least one selected from phenol, o-cresol and p-cresol. The tertiary alkanol is preferably tert-butanol and/or 2,4, 4-trimethyl-2-hydroxypentane, and the tertiary alkaryl alcohol is preferably cumyl alcohol and/or C₁～C₄Alkyl substituted cumyl alcohol. The tertiary alkyl chloride is preferably tert-butyl chloride and/or 2,4, 4-trimethyl-2-chloropentane, and the tertiary alkyl aryl chloride is preferably cumyl chloride and/or C₁～C₄Alkyl substituted cumyl chloride. The tertiary alkyl ether is preferably methyl tert-butyl ether, and the tertiary alkyl aryl ether is preferably cumyl methyl ether and/or C₁～C₄Alkyl substituted cumyl methyl ether. The tertiary alkyl ester is preferably at least one of tert-butyl acetate, 2,4, 4-trimethyl-2-hydroxypentyl acetate, tert-butyl monochloroacetate, 2,4, 4-trimethyl-2-hydroxypentyl monochloroacetate, tert-butyl dichloroacetate, 2,4, 4-trimethyl-2-hydroxypentyl dichloroacetate, tert-butyl trichloroacetate and 2,4, 4-trimethyl-2-hydroxypentyl trichloroacetate, and the tert-alkylaryl ester is preferably selected from the group consisting of cumyl acetate, cumyl monochloroacetate, cumyl dichloroacetate, cumyl trichloroacetate, C-cumyl monochloroacetate₁～C₄Alkyl-substituted cumyl acetate, C₁～C₄Alkyl-substituted cumyl monochloroacetate, C₁～C₄Alkyl-substituted cumyl dichloroacetate and C₁～C₄At least one alkyl-substituted cumyl trichloroacetate.

The multifunctional initiator may be selected from at least one of diphenyltetracumyl chloride, 1, 4-bis (2-chloro-2-propyl) benzene, 5-tert-butyl-1, 3-bis (1-acyloxy-1-methylethyl) benzene, 5-tert-butyl-1, 3-bis (1-methoxy-1-methylethyl) benzene, 1,3, 5-tricumyl chloride, 5-tert-butyl-1, 3-dicumyl ethyl ester, p-dicumyl acetate, p-dicumyl alcohol, 5-tert-butyl-1, 3-dicumyl alcohol, p-dicumyl methyl ether and 5-tert-butyl-1, 3-dicumyl methyl ether, preferably at least one selected from the group consisting of diphenyltetracumyl chloride, 1, 4-bis (2-chloro-2-propyl) benzene, 5-tert-butyl-1, 3-bis (2-chloro-2-propyl) benzene, p-dicumyl methyl ether, p-dicumyl acetate, 5-tert-butyl-1, 3-bis (1-acyloxy-1-methylethyl) benzene and 5-tert-butyl-1, 3-bis (1-methoxy-1-methylethyl) benzene.

The co-initiator may be a lewis acid, preferably selected from at least one of halides, alkyl halides and alkoxy halides of boron, aluminum, titanium, zinc, tin, iron, more preferably selected from at least one of boron trifluoride, titanium tetrachloride, tin tetrachloride, iron trichloride, boron trichloride, aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, isobutylaluminum dichloride and diisobutylaluminum monochloride, and most preferably selected from at least one of titanium tetrachloride, tin tetrachloride, iron trichloride, boron trichloride, aluminum trichloride and ethylaluminum dichloride.

The reaction medium may be an alkane and/or a halogenated hydrocarbon. Wherein, specific examples of the alkane include, but are not limited to: at least one of pentane, hexane, heptane, octane, cyclohexane and methylcyclohexane. Specific examples of the halogenated hydrocarbon include, but are not limited to: at least one of monochloromethane, dichloromethane, trichloromethane, difluoromethane, trifluoromethane, dichloroethane, tetrafluoroethane, pentafluoroethane, hexafluoropropane, trifluoropropane, tetrafluoropropane and hexafluorobenzene.

The sequential active cationic copolymerization is carried out in the presence of an additive, wherein the additive can be an oxygen-containing compound and/or a nitrogen organic compound, and is preferably at least one selected from ether compounds, ketone compounds, ester compounds, amine compounds and alcohol compounds. Specific examples of the ether compound include, but are not limited to: at least one of diethyl ether, tetrahydrofuran and dioxane. Specific examples of the ketone compound include, but are not limited to: at least one of acetone, butanone, pentanone, hexanone, and cyclohexanone. Specific examples of the ester compound include, but are not limited to: at least one of methyl acrylate, methyl benzoate, ethyl benzoate, dimethyl phthalate and diisooctyl phthalate. Specific examples of the amine compound include, but are not limited to: at least one of N, N-dimethylformamide, N-dimethylacetamide, pyridine, picoline, 2, 6-dimethylpyridine, 2, 6-di-tert-butylpyridine, piperidine, diethylamine, triethylamine and triphenylamine. Specific examples of the alcohol compounds include, but are not limited to: at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, hexanediol, n-heptanol, isoheptanol, t-heptanol, n-octanol, isooctanol, cyclooctanol, t-octanol, n-nonanol, isononanol, cyclononanol, n-decanol, isodecanol, decanol, decanediol, benzyl alcohol, and phenethyl alcohol. Preferably, the additive is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, pyridine, picoline, 2, 6-lutidine, 2, 6-di-tert-butylpyridine, piperidine, N-propanol, isopropanol, N-butanol, and isobutanol, and particularly preferably from at least one of isopropanol, pyridine, 2, 6-lutidine, piperidine, N-dimethylacetamide, and N, N-dimethylformamide.

In the sequential active cation copolymerization reaction process, the total concentration of the monomers in the reaction system can be 0.5-2.5 mol/L, preferably 0.7-2.0 mol/L, and more preferably 0.9-1.6 mol/L. The molar ratio of the initiator to the co-initiator to the isobutylene can be 1 (1-18) to (60-980), preferably 1 (1-16) to (70-950), and more preferably 1 (1-14) to (80-920). The above molar ratios are related to the molecular weight and the copolymerization composition of the copolymerization product.

The conditions of the sequential active cation copolymerization reaction generally comprise that the temperature can be-60 to-100 ℃, preferably-65 to-95 ℃, more preferably-70 to-90 ℃, and the time can be 0.1 to 2 hours, preferably 0.3 to 1.5 hours, more preferably 0.4 to 1 hour. The polymerization time is temperature dependent, the lower the temperature the shorter the time, and the higher the molecular weight the longer the polymerization time is, depending on the molecular weight of the polymer segment.

In step S1, after the sequential living cationic copolymerization is completed, the method generally further includes adding a terminating agent to the living chain of the block copolymer to terminate the reaction, mixing the terminated reaction system with a poor solvent and flocculating and separating out, separating to obtain a copolymerization product, washing and purifying the copolymerization product with ethanol for multiple times, and drying the copolymer in a vacuum drying oven at 50 ℃ to constant weight to obtain a dried block copolymer. Wherein the terminator and the poor solvent may each be independently selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone, preferably each be independently selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, water, acetone, and butanone, and most preferably each be independently selected from at least one of methanol, ethanol, water, and butanone.

In step S2, the brominating reagent is preferably bromine, and the bromination/chlorination reaction is carried out in the presence of a bromination/chlorination initiator. Specifically, the block copolymer obtained in step S1 is dissolved in a solvent, a bromination/chlorination initiator and bromine are added to carry out a bromination reaction, after the reaction is completed, a small amount of aqueous sodium hydroxide solution is added to the system to carry out a neutralization reaction, the neutralized reaction system is mixed with a poor solvent and flocculated out, the brominated/chlorinated copolymer is obtained by separation, and after the copolymer is washed and purified by ethanol, the copolymer is dried in a vacuum drying oven at 50 ℃ to constant weight, so that the dried brominated/chlorinated block copolymer is obtained.

The bromination/chlorination initiator may be any of various existing compounds capable of generating radicals, and specific examples thereof include, but are not limited to: azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, preferably at least one selected from azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, and cumene hydroperoxide, more preferably azobisisobutyronitrile and/or azobisisoheptonitrile.

In step S2, the solvent for dissolving the block copolymer may be selected from at least one of pentane, hexane, heptane, octane, cyclohexane, and methylcyclohexane, preferably from at least one of pentane, cyclohexane, n-hexane, and methylcyclohexane, and more preferably from cyclohexane and/or n-hexane.

The bromination/chlorination reaction conditions in the present invention are not particularly limited, and for example, the bromination/chlorination reaction conditions generally include a molar ratio of p-methylstyrene structural units to bromine/chlorine (0.40 to 3):1, preferably (0.45 to 2.5):1, and more preferably (0.48 to 2.0):1, and the temperature may be 50 to 150 ℃, preferably 60 to 120 ℃, more preferably 70 to 100 ℃, and the time may be 0.5 to 2.5 hours, preferably 0.8 to 2.0 hours, and more preferably 1.0 to 1.5 hours. The reaction temperature and reaction time are dependent on the bromination/chlorination initiator selected.

The poor solvent for flocculating the brominated/chlorinated copolymer in step S2 may be selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone, preferably from at least one of methanol, ethanol, n-propanol, isopropanol, water, acetone, and butanone, more preferably from at least one of methanol, ethanol, water, and butanone.

In step S3, the nitrogen onium ion-functionalized/phosphorus onium ion-functionalized method may be a solution method or a melt method.

When the solution method is used for the azonium ion-functionalization/phosphonium ion-functionalization, the following steps are included: dissolving the brominated/chlorinated block copolymer in a solvent, and adding a nitrogen onium ionizing reagent and/or a phosphonium ionizing reagent for ionization reaction to obtain the brominated/chlorinated nitrogen onium/phosphonium ion salt substituted styrene block copolymer. Wherein, the concentration of the brominated/chlorinated block copolymer in the reaction system can be 10-200 g/L, preferably 15-100 g/L, and more preferably 20-70 g/L. The molar ratio of benzyl bromide/benzyl chloride to the nitrogen onium ionizing agent and/or the phosphorus onium ionizing agent in the brominated/chlorinated block copolymer can be (1-5): 1, preferably (1-4): 1, and more preferably (1-3): 1. When only the nitrogen onium ionizing agent or the phosphorus onium ionizing agent is used, the molar ratio of the bromomethyl group/chloromethyl group to the nitrogen onium ionizing agent and/or the phosphorus onium ionizing agent in the brominated/chlorinated block copolymer means the molar ratio of the bromomethyl group/chloromethyl group to the nitrogen onium ionizing agent or the phosphorus onium ionizing agent in the brominated/chlorinated block copolymer; when both a nitrogen onium ionizing agent and a phosphorus onium ionizing agent are used, the molar ratio of bromomethyl/chloromethyl group to the nitrogen onium ionizing agent and/or the phosphorus onium ionizing agent in the brominated/chlorinated block copolymer means the molar ratio of bromomethyl/chloromethyl group to the total amount of the nitrogen onium ionizing agent and the phosphorus onium ionizing agent in the brominated/chlorinated block copolymer. The solvent may be a mixed solvent of halogenated alkane and at least one of N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide (the volume ratio of the halogenated alkane to the N, N-dimethylformamide to the N, N-dimethylacetamide is preferably 5 (0.1-1)). In addition, the ionization reaction conditions generally include a temperature of 0 to 95 ℃, preferably 10 to 90 ℃, and more preferably 25 to 80 ℃, and a time of 0.1 to 72 hours, preferably 0.5 to 48 hours, and more preferably 1 to 24 hours. The temperature and time of the ionization reaction depend on the requirements of the degree of nitrogen/phosphorus ionization, which is higher the temperature or the longer the time.

When the azonium ion functionalization and/or phosphonium ion functionalization is carried out using a melt process, the following steps are included: and (3) carrying out melt blending on the brominated/chlorinated block copolymer, a nitrogen onium ionizing agent and/or a phosphonium ionizing agent and an oxygen-containing nitrogen-containing additive to obtain the nitrogen onium/phosphonium ion salt substituted styrene block copolymer. The melt blending condition generally includes a temperature of 100-240 ℃, preferably 120-230 ℃, more preferably 130-220 ℃, and a time of 1-18 min, preferably 2-15 min, more preferably 3-10 min. The temperature and time of the ionization reaction depend on the requirements of the degree of nitrogen or phosphonium ionization, which is higher the temperature or the longer the time required.

The azonium ionizing agent preferably has a structure represented by formula (6), and the phosphonium ionizing agent preferably has a structure represented by formula (7):

wherein R is₁～R₇Each independently is H, C₁～C₂₀Alkyl or C₆～C₂₀Preferably each independently is C₁～C₁₅Alkyl or C₆～C₁₅More preferably each independently is C₁～C₁₀Alkyl of (C)₆～C₁₀Phenyl or alkyl substituted phenyl.

Specifically, the azonium ionizing agent is an imidazole compound, and specific examples thereof include, but are not limited to: at least one of imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, N-benzylimidazole, phenylimidazole, 1-ethylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 1, 2-dimethylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole and 2, 4-diphenylimidazole, preferably at least one selected from the group consisting of imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, N-benzylimidazole and phenylimidazole, and more preferably at least one selected from the group consisting of imidazole, N-methylimidazole, N-butylimidazole and N-benzylimidazole. The phosphonium ionizing agent is an organophosphine compound, and specific examples thereof include, but are not limited to: trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, triisobutyl phosphine, tri-tert-butyl phosphine, triphenyl phosphine, triisopropyl phosphine, diphenylmethyl phosphine, diphenylpropyl phosphine, diphenylisobutyl phosphine, diphenyl-n-butyl phosphine, dimethylphenyl phosphine, diethylphenyl phosphine, dipropylphenyl phosphine, and dibutyl phenyl phosphine, and preferably at least one selected from tripropyl phosphine, triisopropyl phosphine, triisobutyl phosphine, tri-tert-butyl phosphine, triphenyl phosphine, and diphenylmethyl phosphine.

Specific examples of the oxygen-containing and nitrogen-containing additive include, but are not limited to: 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-alpha-aniline, 3-hydroxybutyraldehyde-alpha-naphthylamine, 4-octyldiphenylamine, N-diphenylethylenediamine, p-diaminodiphenylamine, 4 '-bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymers, 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol ester, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2' -thiobis (4-methyl-6-tert-butylphenol), 2, 2-methylenebis (4-methyl-alpha-methylcyclohexyl) phenol, tris (3, 5-di-tert-butyl-4-hydrozylbenzylisocyanurate), nickel dithiocarbamate, diethyl 3,5' -di-tert-butyl-4-hydrozylbenzylphosphonate, cyclohexyl-N ' -phenylphenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenylphenylenediamine, 2' -methylenebis (4-ethyl-6-tert-butylphenol), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydrozylbenzyl) benzene, 2-mercaptobenzothiazole, zinc 2-mercaptobenzothiazole, carbodiimide and N-isopropyl-N ' -phenylphenylenediamine Preferably at least one selected from the group consisting of 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-alpha-aniline, 3-hydroxybutyraldehyde-alpha-naphthylamine, 4-octyldiphenylamine, N-diphenylethylenediamine, p-diaminodiphenylamine, 4' -bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymers, 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol esters and octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, more preferably 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, 2, 4-trimethyl-1, 2-dihydroquinoline, 3-hydroxybutyraldehyde- α -naphthylamine, 4' bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, pentaerythritol ester and octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.

When the solution method is used for the functionalization of the azonium/phosphonium ions, the solvent used may be an alkyl halide, and specifically may be at least one selected from the group consisting of methylene chloride, chloroform, ethyl chloride, ethylene dichloride, ethylene trichloride, ethylene pentachloride, ethylene bromide, ethylene dibromide, ethylene tribromide, ethylene tetrabromide, 1-bromo-2-ethyl chloride, 1-bromo-1-ethyl chloride, 1, 2-dibromo-1, 1-dichloroethane, 1, 2-dibromotetrachloroethane, chloropropane, dichloropropane, trichloropropane, bromopropane, dibromopropane, tribromopropane, 2-bromo-1-chloropropane, 1-bromo-3-chloropropane, 2-chloro-2-bromopropane, chlorobutane, dichlorobutane, bromobutane, dibromobutane, 1-bromo-4-chlorobutane and bromodichlorobutane, preferably at least one selected from the group consisting of dichloromethane, trichloromethane, dichloroethane, dibromoethane, tribromoethane, dichloropropane, trichloropropane, dibromopropane, tribromopropane, chlorobutane and dichlorobutane, more preferably at least one selected from the group consisting of dichloromethane, trichloromethane, dichloroethane, dibromoethane and dibromobutane.

In step S3, the amine group functionalization method may be that the brominated block copolymer undergoes an amination reaction in the presence of an amination reagent and a reaction medium, and then hydrazine hydrate is added to perform a reduction reaction (in order to reduce phthalimide groups to primary amines, the reduction reaction conditions include a temperature of 100 to 110 ℃ and a time of 5 to 10 hours, after the reaction is completed, an alkane solvent is added and stirred for 20 to 40 minutes, water is added, the mixture is transferred to a separating funnel for extraction, an upper layer substance and a poor solvent are mixed and flocculated out, the obtained precipitate is washed and dried to obtain the amine group functionalized styrene block copolymer, wherein the amination reagent is preferably potassium phthalimide, the reaction medium is preferably a mixed solvent of tetrahydrofuran and at least one of nitrogen methyl pyrrolidone, nitrogen ethyl pyrrolidone, nitrogen propyl pyrrolidone and nitrogen butyl pyrrolidone, more preferably a mixed solvent of tetrahydrofuran and at least one of azomethylpyrrolidone, azoethylpyrrolidone and azopropylpyrrolidone, and most preferably a mixed solvent of tetrahydrofuran and azomethylpyrrolidone. The poor solvent may be selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone, preferably from at least one of methanol, ethanol, n-propanol, isopropanol, water, acetone, and butanone, and more preferably from at least one of methanol, ethanol, water, and butanone. The amination reaction conditions generally include that the temperature can be 50-120 ℃, preferably 60-110 ℃, more preferably 70-100 ℃, and the time can be 1-36 hours, preferably 2-30 hours, more preferably 3-24 hours. The temperature and time for the functionalization of the pendant amine groups will depend on the degree of functionalization desired for the pendant amine groups, with higher degrees of functionalization being either higher temperatures or longer times.

In step S3, the hydroxyl group functionalization method may be to perform a hydrolysis reaction on the brominated/chlorinated block copolymer in the presence of an alkaline substance and a reaction medium, after the reaction is completed, add an alkane solvent and stir for 20-40 min, add water, transfer the mixture to a separating funnel for extraction, mix an upper layer substance with a poor solvent and flocculate and separate out, wash and dry the obtained precipitate, and obtain the hydroxyl group functionalized styrene block copolymer. Among them, the alkali substance is preferably sodium hydroxide and/or potassium hydroxide. The reaction medium is preferably a mixed solvent of tetrahydrofuran and at least one of azomethylpyrrolidone, azoethylpyrrolidone, azopropylpyrrolidone and azobutylpyrrolidone, more preferably a mixed solvent of tetrahydrofuran and at least one of azomethylpyrrolidone, azoethylpyrrolidone and azopropylpyrrolidone, and most preferably a mixed solvent of tetrahydrofuran and azomethylpyrrolidone. The poor solvent may be selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone, preferably from at least one of methanol, ethanol, n-propanol, isopropanol, water, acetone, and butanone, and more preferably from at least one of methanol, ethanol, water, and butanone. In addition, the hydrolysis reaction conditions generally include a temperature of 50 to 150 ℃, preferably 60 to 120 ℃, more preferably 70 to 100 ℃, and a time of 1 to 36 hours, preferably 2 to 30 hours, more preferably 3 to 24 hours. The temperature and time of pendant hydroxyl functionalization depends on the degree of pendant hydroxyl functionalization desired, with higher degrees of functionalization being either higher temperatures or longer times.

The styrene block copolymer prepared by the method has the advantages that the physical and mechanical properties, the dynamic and mechanical properties, the hydrophilic and hydrophobic properties, the polarization degree and the like of the material can be regulated and controlled by the structural content of the copolymer, the sources of monomer raw materials are wide, and the production cost is reduced. After the styrene block copolymer is subjected to functionalization reaction, the rigidity, the glass transition temperature of a hard segment, the tensile strength and the service temperature of the material can be obviously improved, even the functionalized styrene block copolymer can become a hydrophilic thermoplastic elastomer, and the self-repairing performance of the functionalized styrene block copolymer material is further improved.

The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.

In the following examples and comparative examples, analytical methods were used:

(1) the molecular weight and the hard segment content are respectively characterized by adopting a gel permeation chromatography and a nuclear magnetic resonance spectrometer:

A. gel Permeation Chromatography (GPC) method: the gel permeation chromatograph with the model number of Waters 1515 is adopted for testing, the solvent is tetrahydrofuran, PS is a standard sample, and the temperature is 30 ℃.

B. Nuclear magnetic resonance (¹H NMR) method: the test is carried out by adopting a Bruker Avance 400MHz liquid nuclear magnetic resonance instrument, using deuterated chloroform as a solvent and carrying out the test at room temperature.

(2) The bromination degree is tested by a nuclear magnetic resonance spectrometer: the test was carried out at 25 ℃ using a Bruker Avance 400MHz liquid NMR spectrometer with deuterated chloroform as solvent.

(3) The structure and performance of the FSMB are tested by water contact angle, TGA, DMA, POM and mechanical properties.

A. Water contact angle: the water contact angle is tested by a method of measuring the water contact angle by using a JC2000D2M type contact angle measuring instrument by placing the sample on a film pressing machine and hot-pressing the sample into a film at a certain temperature, and the parallel test is carried out for 3 times.

B. Dynamic Mechanical Analysis (DMA): and testing by adopting a dynamic mechanical analyzer with the model number of TA-Q800. During testing, the sample prepared by the test is pressed into a film by a film pressing machine at a proper temperature, and then a standard sample strip is prepared. The test mode is a stretching mode, the temperature range is-100-180 ℃, the heating rate is 10 ℃/min, the test frequency is 10Hz, and the deformation amount is 0.1%.

C. Phase contrast microscope (POM): a cross-shaped knife edge is cut by a blade from a film formed by the sample, and the shape of the sample is observed by an OLYMPUS BX-51 phase contrast microscope at room temperature and certain time intervals.

D. And (3) testing mechanical properties: and (3) testing an I-type sample according to the GBT528-2009 standard, wherein the tensile rate is 50mm/min, and the sample is tested by using an electronic universal testing machine with the model of 3345.

Example 1

This example illustrates the preparation and performance of a azonium ionized poly [ (p-methylstyrene-co-styrene) -b-isobutylene-b- (styrene-co-p-methylstyrene) ] block copolymer (FSMB-1).

Preparation of S1 and SMB-1

Under the protection of high-purity nitrogen and at the temperature of minus 78 ℃, 110mL of dichloromethane, 164mL of normal hexane, 0.3mol of Isobutene (IB) and 0.845mmol of bifunctional initiator 1, 4-bis (2-chloro-2-propyl) benzene (DCC) are added into a polymerization reactor, and 7.0mL of FeCl containing co-initiator is added₃With an additive isopropanol (POH) solution (wherein: FeCl₃POH 1:1.4) so that the IB concentration in the reaction system is 1.0mol/L, DCC FeCl₃IB (molar ratio) is 1:3.6:355, the reaction is carried out for 15min, and the IB monomer is completely converted to obtain a polyisobutylene double-end active chain; adding 100mL of mixed solution containing styrene (St, 68.7mmol) and p-methylstyrene (pMS, 34.4mmol) in dichloromethane/n-hexane (4/6, v/v), and further carrying out active cationic block copolymerization reaction for 30min to obtain a double-end active chain of the poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene); adding 30mL of ethanol to terminate the reaction, mixing the terminated reaction system with the ethanol, flocculating and separating out, washing and purifying the mixture by using the ethanol for 3 times, and drying the copolymer in a vacuum drying oven at 50 ℃ to constant weight to obtain dry SMB-1.

S2 preparation of BSMB-1

50g of the above SMB-1 sample was dissolved in 500mL of cyclohexane, and 100mg of azobisisoheptonitrile and bromine (Br) were added in this order₂) So that pMS is Br₂1:1 (molar ratio), reacting at 65 ℃ for 1 h; adding a small amount of sodium hydroxide aqueous solution into the system for neutralization reaction; the reaction product was worked up as in S1 to give dry BSMB-1.

S3 preparation of FSMB-1

8g of the BSMB-1, 4.8mmol of N-Methylimidazole (MI) and 100mg of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed so that BBr: MI is 2.6:1 (molar ratio), and the mixture is melted and reacted for 5min at 150 ℃ to obtain the methylimidazolium ionized SMB (FSMB-1) with a side group containing a methylimidazolium ionic group, wherein the structural formula of the methylimidazolium ionized SMB is shown as the formula (1) and (2). Wherein n is 338, the total number of m is 8.8% of the total number of moles of all structural units, the total number of p is 11.2% of the total number of moles of all structural units, the total number of q is 7.6% of the total number of moles of all structural units, and the total number of r is 5.0% of the total number of moles of all structural units.

The prepared FSMB-1 functionalized styrene triblock copolymer has the tensile strength of 3.2MPa and the elongation at break of 25 percent; the glass transition temperature of the hard chain segment is 154 ℃, the storage modulus (G') at normal temperature (25 ℃) is 486MPa, the storage modulus at 160 ℃ is still 1.7MPa, the water contact angle is 72 degrees, the hard chain segment is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the membrane material are completely self-repaired after being placed for 10 hours at 50 ℃.

Compared with the functionalized styrene triblock copolymer without side groups shown in the comparative example 1(SMB-1), the prepared functionalized styrene triblock copolymer FSMB-1 has the advantages that the glass transition temperature of a hard chain segment is increased by 29 ℃, the tensile strength is increased by 14.3 percent and the elongation at break is increased by 25.0 percent due to the side group functionalization (q + r) degree of 12.6 percent; the storage modulus at 25 ℃ is improved by 113MPa, which shows that the rigidity of the material is improved by 30.3 percent, and the service temperature is also improved by about 30 ℃; due to the existence of the methylimidazolium ion group contained in the 5.0 percent of side group, the water contact angle of the surface of the triblock copolymer film material is reduced by 25 degrees, the hydrophobic material is changed into the hydrophilic material, the self-repairing speed of the material is accelerated, and the self-repairing time at the same temperature is shortened by 5 hours.

Example 2

S1 and SMB-2 are prepared in the same manner as in step S1 of example 1. Under the protection of high-purity nitrogen at the temperature of minus 80 ℃, 220mL of dichloromethane, 328mL of normal hexane, 0.6mol of isobutene and 3.38mmol of DCC are added into a polymerization reactor and mixed evenly, 14mL of FeCl containing a coinitiator is added₃With a POH solution (wherein: FeCl₃POH 1:1.4) so that the IB concentration in the reaction system is 1.0mol/L, DCC FeCl₃IB (molar ratio) of 1:3.6:178, polymerization reaction for 15min, and complete conversion of IB monomer to obtain polyisobutylene with double endsAn active chain; except that the amount of the mixed solution of St and pMS was decreased, 120mL of a mixed solution of dichloromethane/n-hexane (4/6, v/v) containing 82.4mmol of styrene and 41.2mmol of p-methylstyrene was added to obtain poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene) triblock copolymer SMB-2.

S2 and BSMB-2 were prepared in the same manner as in step S2 of example 1, except that Br was added₂The amount of added BSMB-2 was increased (pMS: Br (molar ratio) ═ 1:1.5) for a reaction time of 50 min.

S3 and FSMB-2 were prepared according to the same procedure as in step S3 of example 1 except that BBr: MI was 1.4:1 (molar ratio), and reacted at 130 ℃ for 6min to obtain methylimidazolium-ionized SMB (FSMB-2) having the structural formulae (1) and (2). Wherein n has an average value of 462, the total number of m is 2.2% of the total number of moles of all the structural units, the total number of p is 7.6% of the total number of moles of all the structural units, the total number of q is 2.0% of the total number of moles of all the structural units, and the total number of r is 5.0% of the total number of moles of all the structural units.

The G 'of the prepared FSMB-2 at normal temperature (25 ℃) is 311MPa, the G' at 155 ℃ is 0.9MPa, the glass transition temperature of a hard chain segment is 147 ℃, the tensile strength is 2.1MPa, the elongation at break is 46%, the water contact angle of the film is 75 degrees, the film is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the film material are placed for 6 hours at room temperature for self-repairing.

Compared with the functionalized styrene triblock copolymer without side groups shown in the comparative example 2(SMB-2), the prepared functionalized styrene triblock copolymer FSMB-2 has the advantages that the glass transition temperature of a hard chain segment is improved by 34 ℃, the tensile strength is improved by 16.7 percent and the elongation at break is improved by 24.3 percent because the degree of side group functionalization (q + r) is 7.0 percent; the storage modulus at 25 ℃ is improved by 112MPa, which shows that the rigidity of the material is improved by 56.6 percent, and the service temperature is also improved by about 34 ℃; due to the existence of the methylimidazolium ion group contained in the 5.0 percent of side group, the water contact angle of the surface of the triblock copolymer film material is reduced by 24 degrees, the hydrophobic material is changed into the hydrophilic material, the self-repairing rate of the material is accelerated, and the amplitude is increased by 33 percent.

Example 3

S1, SMB-1 is prepared in the same way as the step S1 in the example 1;

s2, BSMB-1 was prepared in the same manner as in step S2 of example 1;

s3, FSMB-3 was prepared as in step S3 of example 1 except that MI was added such that BBr: MI was 1:1 (molar ratio), the reaction temperature was 160 ℃ and the time was 7min to obtain methylimidazolium ionized SMB (FSMB-3) of the formula (1) and (2). Wherein n has an average value of 338, the total number of m is 8.8% of the total number of moles of all structural units, the total number of p is 11.2% of the total number of moles of all structural units, the total number of q is 0.1% of the total number of moles of all structural units, and the total number of r is 12.5% of the total number of moles of all structural units.

The G 'of the prepared FSMB-3 at normal temperature (25 ℃) is 551MPa, the G' at 170 ℃ is 1.1MPa, the glass transition temperature of a hard chain segment is 161 ℃, the tensile strength is 3.6MPa, the elongation at break is 34%, the water contact angle is 61 degrees, the material is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the film material are self-repaired after being placed at the room temperature (25 ℃) for 8 hours.

Compared with the functionalized styrene triblock copolymer without side groups shown in the comparative example 1(SMB-1), the prepared functionalized styrene triblock copolymer FSMB-3 has the advantages that the glass transition temperature of a hard chain segment is increased by 36 ℃, the tensile strength is increased by 28.6 percent, and the elongation at break is increased by 70.0 percent because the degree of (r) functionalization of the methyl imidazolium ion-containing side group is 12.5 percent; the storage modulus at 25 ℃ is improved by 178MPa, which shows that the rigidity of the material is improved by 47.7 percent, and the service temperature is also improved by about 40 ℃; the water contact angle is reduced by 36 degrees, the hydrophobic material is changed into the hydrophilic material, the self-repairing speed of the material is accelerated, the self-repairing temperature is reduced by 25 ℃, and the self-repairing speed is increased by 46.7 percent.

Example 4

Preparation of S1 and SMB-4

SMB-4 was prepared in the same manner as in step S1 of example 1, except that the amount of the initiator used was reduced to DCC: FeCl₃IB (molar ratio) is 1:9:888, the first stage polymerization reaction time is 30min, and the second stage polymerization reaction time is 60min, so that the SMB-4 is obtained.

Preparation of S2 and BSMB-4

BSMB-4 was prepared in the same manner as in step S2 of example 1, except that pMS: Br was used₂1:1 (molar ratio), the reaction temperature is 70 ℃, and the reaction time is 40min, so as to obtain the BSMB-4.

S3 preparation of FSMB-4

BSMB-4 was prepared according to the same procedure as in step S3 of example 1, except that BBr: MI ═ 4:3 (molar ratio), 100mg of octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate was added and reacted at 150 ℃ for 6min to obtain methylimidazolium-ionized SMB (FSMB-4) having the structural formulae (1) and (2). Wherein n has an average value of 842, the total number of m is 23.0% of the total number of moles of all the structural units, the total number of p is 5.0% of the total number of moles of all the structural units, the total number of q is 1.1% of the total number of moles of all the structural units, and the total number of r is 3.0% of the total number of moles of all the structural units.

The G 'of the prepared FSMB-4 at normal temperature (25 ℃) is 411MPa, the G' at 165 ℃ is 0.9MPa, the glass transition temperature of a hard chain segment is 150 ℃, the tensile strength is 3.1MPa, the elongation at break is 40%, the water contact angle is 83 degrees, the material is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the film material are placed for 4 hours at 50 ℃ for self-repairing.

Compared with the functionalized styrene triblock copolymer without the side group shown in the comparative example 3(SMB-4), the prepared functionalized styrene triblock copolymer FSMB-4 has the advantages that the glass transition temperature of a hard chain segment is improved by 24 ℃, the tensile strength is improved by 24.0 percent, and the elongation at break is improved by 17.6 percent because the degree of the side group functionalization (q + r) is 4.1 percent; the storage modulus at 25 ℃ is improved by 150MPa, which shows that the rigidity of the material is improved by 57.5 percent, and the service temperature is also improved by about 30 ℃; due to the existence of the methylimidazolium ion group contained in the 3.0 percent of side group, the water contact angle of the surface of the triblock copolymer film material is reduced by 18 degrees, so that the material is changed from a hydrophobic material to a hydrophilic material, the self-repairing rate of the material is accelerated, and the amplitude is increased by 33.3 percent.

Example 5

Preparation of S1 and SMB-5

SMB-5 was prepared in the same manner as in step S1 of example 1, except that the amount of the initiator was decreased, the amount of the St and MS mixed solution was increased, and the DCC: FeCl was added₃IB 1:12.5:900 (molar ratio), SMB-5 was obtained.

Preparation of S2 and BSMB-5

BSMB-5 was prepared in the same manner as in step S2 of example 1, except that Br was increased₂In such an amount that pMS: Br₂4:3 (molar ratio), reaction temperature 68 ℃, reaction time 45min, to obtain BSMB-5.

S3 preparation of FSMB-5

BSMB-5 was prepared as in step S3 of example 1, except that the functionalizing agent was Benzylimidazole (BI) such that BBr: BI is 3:2 (molar ratio) and reacted at 150 ℃ for 5min to give benzylimidazolium ionized SMB (FSMB-5) of the formula (1) and (2). Wherein n has an average value of 958, the total number of m is 19.0% of the total number of moles of all the structural units, the total number of p is 5.1% of the total number of moles of all the structural units, the total number of q is 2.2% of the total number of moles of all the structural units, and the total number of r is 4.0% of the total number of moles of all the structural units.

The G 'of the prepared FSMB-5 at normal temperature (25 ℃) is 431MPa, the G' at 159 ℃ is 1.0MPa, the glass transition temperature of a hard chain segment is 151 ℃, the tensile strength is 4.2MPa, the elongation at break is 51 percent, the water contact angle of the film is 81 degrees, the film is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the film material are placed for 8 hours at room temperature for self-repairing.

Compared with the functionalized styrene triblock copolymer without the side group shown in the comparative example 4(SMB-5), the prepared functionalized styrene triblock copolymer FSMB-5 has the advantages that the glass transition temperature of a hard chain segment is improved by 28 ℃, the tensile strength is improved by 23.5 percent, and the elongation at break is improved by 21.4 percent because the degree of the side group functionalization (q + r) is 6.2 percent; the storage modulus at 25 ℃ is improved by 130MPa, which shows that the rigidity of the material is improved by 43.2 percent, and the service temperature is also improved by about 29 ℃; because 4.0 percent of lateral group contains benzyl imidazolium ion group, the water contact angle of the surface of the triblock copolymer film material is reduced by 24 degrees, the hydrophobic material is changed into the hydrophilic material, the self-repairing speed of the material is accelerated, and the amplitude is increased by 20 percent.

Example 6

Preparation of S1 and SMB-6

SMB-6 was prepared in the same manner as in step S1 of example 1. Under the protection of high-purity nitrogen at-78 ℃, 220mL of dichloromethane, 328mL of normal hexane, 0.6mol of isobutene and 3.38mmol of DCC are added into a polymerization reactor and mixed evenly, 14mL of FeCl containing a coinitiator is added₃With a POH solution (wherein: FeCl₃:POH＝1:1.4)，DCC:FeCl₃IB: 1:1.8:177 (molar ratio), after 10min of polymerization, 200mL of a pre-cooled mixed solution containing 137.4mmol of styrene and 68.7mmol of p-methylstyrene, dichloromethane/hexane (4/6, v/v), was added, and after 30min of polymerization, 40mL of ethanol was added to terminate the reaction. Obtaining the SMB-6.

Preparation of S2 and BSMB-6

BSMB-6 was prepared in the same manner as in step S2 of example 1, except that Br was increased₂In such an amount that pMS: Br₂The BSMB-6 was obtained at 70 ℃ for 50min (molar ratio) 3: 2.

S3 preparation of FSMB-6

BSMB-6 was prepared according to the same procedure as in step S3 of example 1, except that the functionalizing agent was triphenylphosphine (P) and Br: P was 6:5 (molar ratio), and 100mg of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester was added and reacted at 150 ℃ for 5min to obtain triphenylphosphine-ionized SMB (FSMB-6) having the structural formulae (1) and (2). Wherein n has an average value of 306, the total number of m accounts for 8.0% of the total moles of all the structural units, the total number of p accounts for 6.8% of the total moles of all the structural units, the total number of q accounts for 1.0% of the total moles of all the structural units, and the total number of r accounts for 5.0% of the total moles of all the structural units.

The G 'of the prepared FSMB-6 at normal temperature (25 ℃) is 511MPa, the G' at 165 ℃ is 1.8MPa, the glass transition temperature of a hard chain segment is 155 ℃, the tensile strength is 3.5MPa, the elongation at break is 31 percent, the water contact angle of the film is 78 degrees, the film is a hydrophilic thermoplastic elastomer material, and scratches on the surface of the film material are placed for 10 hours at room temperature for self-repairing.

Compared with the functionalized styrene triblock copolymer without the side group shown in the comparative example 5(SMB-6), the prepared functionalized styrene triblock copolymer FSMB-6 has the advantages that the glass transition temperature of a hard chain segment is improved by 33 ℃, the tensile strength is improved by 20.7 percent, and the elongation at break is improved by 47.6 percent because the degree of the side group functionalization (q + r) is 6.0 percent; the storage modulus at 25 ℃ is improved by 150MPa, which shows that the rigidity of the material is improved by 41.6 percent, and the service temperature is also improved by about 33 ℃; because 5.0 percent of lateral groups contain triphenylphosphine onium ion groups, the water contact angle of the surface of the triblock copolymer film material is reduced by 29 degrees, the hydrophobic material is changed into the hydrophilic material, the self-repairing speed of the material is accelerated, and the amplitude is increased by 28.6 percent.

Example 7

Preparation of S1 and SMB-7

SMB-7 was prepared in the same manner as in step S1 of example 1, except that the amount of the initiator was decreased, the amount of the St and MS mixed solution was increased, and the DCC: FeCl was added₃IB 1:1.8:90 (molar ratio), SMB-7 was obtained.

Preparation of S2 and BSMB-7

BSMB-6 was prepared in the same manner as in step S2 of example 1, except that Br was increased₂In such an amount that pMS: Br₂1:2 (molar ratio), reaction temperature 75 ℃, reaction time 1.2h, to give BSMB-7.

S3 preparation of FSMB-7

Dissolving 10g of BSMB-7 in 20mL of tetrahydrofuran and 10mL of nitrogen methyl pyrrolidone, adding 2g of KOH/water solution, condensing and refluxing for 24h at 70 ℃, adding 500mL of cyclohexane for dilution, transferring the mixed solution into a separating funnel, adding 1L of deionized water, mixing the upper layer substance with poor solvent ethanol, flocculating and separating out, and drying the copolymer in a vacuum drying oven at 50 ℃ to constant weight to obtain the hydroxyl functionalized SMB (FSMB-7) with the structural formulas shown as formulas (1) and (2). Wherein n has an average value of 1442, the total number of m is 0.9% of the total number of moles of all the structural units, the total number of p is 1.4% of the total number of moles of all the structural units, the total number of q is 0.5% of the total number of moles of all the structural units, and the total number of r is 5.6% of the total number of moles of all the structural units.

The water contact angle of the prepared FSMB-7 film is 62 degrees, the film is a hydrophilic thermoplastic elastomer material, and scratches of the film are placed for 5 hours at 60 ℃ for self-repairing.

Compared with the hydrophobic material of the functionalized styrene triblock copolymer without the side group shown in the comparative example 6(SMB-7), the prepared hydroxyl functionalized styrene triblock copolymer FSMB-7 has the advantages that the water contact angle of the surface of the triblock copolymer film material is reduced by 36 degrees due to the fact that the degree of the side group hydroxyl functional group (r) of the prepared hydroxyl functionalized styrene triblock copolymer FSMB-7 is 5.6 percent, the hydrophobic material is changed into the hydrophilic material, the self-repairing rate of the material is accelerated, and the amplitude is increased by 28.6 percent.

Example 8

S1 and SMB-8 are prepared by the same method as the step S1 in the example 4;

s2, BSMB-8 is prepared in the same manner as in step S2 of example 4;

s3 preparation of FSMB-8

5g of BSMB-8 was dissolved in 25mL of tetrahydrofuran and 12.5mL of N-methylpyrrolidone, 1.25g of potassium phthalimide was added, and the mixture was condensed and refluxed at 70 ℃ for 5 hours, and 3g of hydrazine hydrate was added to the system and refluxed at 105 ℃ for 8 hours. The post-treatment method was the same as in example 1 to obtain amino-functionalized SMB (FSMB-8) having the structural formulae (1) and (2). Wherein n has an average value of 842, the total number of m is 23.0% of the total number of moles of all the structural units, the total number of p is 5.0% of the total number of moles of all the structural units, the total number of q is 3.1% of the total number of moles of all the structural units, and the total number of r is 1.0% of the total number of moles of all the structural units.

The water contact angle of the prepared FSMB-8 film is 69 degrees, and after the surface of the FSMB-8 film is scratched with a mark, the FSMB-8 film is placed at room temperature for 10 hours, and the mark disappears, which shows that the material is endowed with excellent self-repairing performance.

Compared with the hydrophobic material of the functionalized styrene triblock copolymer without the side group shown in the comparative example 3(SMB-4), the prepared hydroxyl functionalized styrene triblock copolymer FSMB-8 reduces the water contact angle of the surface of the triblock copolymer film material by 32 degrees because the degree of the side group amino functional group (r) is 1.0 percent, so that the material is changed from the hydrophobic material to the hydrophilic material.

Comparative example 1

The G 'of the prepared SMB-1 at the normal temperature of 25 ℃ is 373MPa, the G' at the temperature of 130 ℃ is 0.94MPa, the glass transition temperature of a hard chain segment is 125 ℃, the tensile strength is 2.8MPa, the elongation at break is 20 percent, the water contact angle of the film is 97 degrees, and the material is a hydrophobic thermoplastic elastomer material. And the scratches on the surface of the film material are placed for 15 hours at 50 ℃ for self-repairing.

Comparative example 2

The G 'of the prepared SMB-2 at the normal temperature of 25 ℃ is 198MPa, the G' at the temperature of 125 ℃ is 1.0MPa, the glass transition temperature of a hard chain segment is 113 ℃, the tensile strength is 1.8MPa, the elongation at break is 37 percent, the water contact angle of the film is 99 degrees, and the material is a hydrophobic thermoplastic elastomer material. The scratches on the surface of the film material are placed for 9 hours at room temperature for self-repairing.

Comparative example 3

The prepared SMB-4 has the advantages that G 'at the normal temperature of 25 ℃ is 261MPa, G' at the temperature of 135 ℃ is 0.8MPa, the glass transition temperature of a hard chain segment is 126 ℃, the tensile strength is 2.5MPa, the elongation at break is 34 percent, the water contact angle is 101 degrees, and the material is a hydrophobic thermoplastic elastomer material. And scratches on the surface of the film material are placed for 6 hours at 50 ℃ for self-repairing.

Comparative example 4

The G 'of the prepared SMB-5 film at the normal temperature of 25 ℃ is 301MPa, the G' of the prepared SMB-5 film at the temperature of 130 ℃ is 1.1MPa, the glass transition temperature of a hard chain segment is 123 ℃, the tensile strength is 3.4MPa, the elongation at break is 42 percent, the water contact angle of the SMB-5 film is 105 degrees, and the prepared SMB-5 film is a hydrophobic thermoplastic elastomer material. The scratches on the surface of the film material are placed for 10 hours at room temperature for self-repairing.

Comparative example 5

The G 'of the prepared SMB-6 at the normal temperature of 25 ℃ is 361MPa, the G' at the temperature of 132 ℃ is 1.3MPa, the glass transition temperature of a hard chain segment is 122 ℃, the tensile strength is 2.9MPa, the elongation at break is 21 percent, the water contact angle of the film is 107 degrees, and the material is a hydrophobic thermoplastic elastomer material. The scratches on the surface of the film material are placed for 14h at room temperature for self-repairing.

Comparative example 6

The G 'of the prepared SMB-7 at the normal temperature of 25 ℃ is 300MPa, the G' of the prepared SMB-7 at the normal temperature of 135 ℃ is 1.2MPa, the glass transition temperature of a hard chain segment is 125 ℃, the tensile strength is 2.5MPa, the elongation at break is 24 percent, the water contact angle of the film is 98 degrees, and the material is a hydrophobic thermoplastic elastomer material. And the scratches on the surface of the film are placed for 7 hours at 60 ℃ for self-repairing.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A styrenic block copolymer comprising a polyisobutylene segment having a structure represented by formula (1) and a random copolymer segment of styrene and a substituted styrene having a structure represented by formula (2):

wherein R is₁～R₇Each independently is H, C₁～C₂₀Alkyl or C₆～C₂₀Aryl of, X^-Is chloride ion or bromide ion;

the styrene block copolymer is a linear polymer or a star polymer;

2. The styrenic block copolymer of claim 1 wherein,

n is 250 to 1600;

the total number of m accounts for 0.7-27% of the total mole number of all the structural units;

the total number of p accounts for 0.8-14% of the total mole number of all the structural units;

the total number of q accounts for 0.08-9% of the total mole number of all the structural units;

the total number of r accounts for 0.7-15% of the total mole number of all the structural units;

R₁～R₇each independently is C₁～C₁₅Alkyl or C₆～C₁₅Aryl group of (1).

3. The styrenic block copolymer according to claim 2, wherein n is 300 to 1500; the total number of m accounts for 0.8-25% of the total mole number of all the structural units; the total number of p accounts for 1.0-12% of the total mole number of all the structural units; the total number of q accounts for 0.1-8% of the total mole number of all the structural units; the total number of r accounts for 0.8-13% of the total mole of all the structural units.

4. The styrenic block copolymer of claim 2, wherein the R is₁～R₇Each independently is C₁～C₁₀Alkyl of (C)₆～C₁₀Phenyl or alkyl substituted phenyl.

5. A process for the preparation of styrenic block copolymers according to any of claims 1 to 4, characterized by comprising the following steps:

s3, subjecting the brominated/chlorinated block copolymer obtained in step S2 to pendant azonium ion functionalization, phosphonium ion functionalization, amine group functionalization or hydroxyl group functionalization to obtain the styrenic block copolymer.

6. The production method according to claim 5,

the sequential active cation copolymerization reaction adopts a monofunctional initiator/three-step polymerization reaction and comprises the following steps:

s1-3, adding styrene and p-methylstyrene into the reaction system of the step S1-2, and further initiating the active cationic copolymerization reaction of the styrene and the p-methylstyrene by the active chain of the diblock copolymer obtained in the step S1-2 to obtain the active chain of the poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene) triblock copolymer;

or, the sequential active cation copolymerization adopts a bifunctional or polyfunctional initiator/two-step polymerization reaction, and comprises the following steps:

s2-2, adding styrene and p-methylstyrene into the reaction system of the step S2-1, and further initiating the active cationic copolymerization reaction of the styrene and the p-methylstyrene by the polyisobutylene double-end or multi-end active chain obtained in the step S2-1 to obtain linear poly (styrene-co-p-methylstyrene) -b-polyisobutylene-b-poly (styrene-co-p-methylstyrene) triblock copolymer double-end active chain or star block copolymer multi-end active chain;

the number of the functional groups of the polyfunctional group is 3-8.

7. The method of claim 6, wherein the monofunctional initiator is selected from at least one of water, protonic acid, phenol, tertiary alkanol, tertiary alkyl aryl alcohol, tertiary alkyl chloride, tertiary alkyl aryl chloride, tertiary alkyl ether, tertiary alkyl aryl ether, tertiary alkyl ester and tertiary alkyl aryl ester; the multifunctional initiator is selected from diphenyl tetra-cumyl chloride, 1, 4-bis (2-chloro-2-propyl) benzene, 5-tert-butyl-1, 3-bis (1-acyloxy-1-methylethyl) benzene, 5-tert-butyl-1, 3-bis (1-methoxy-1-methylethyl) benzene, 1,3, 5-tri-cumyl chloride, at least one of 5-tert-butyl-1, 3-dicumyl ethyl ester, p-dicumyl acetate, p-dicumyl alcohol, 5-tert-butyl-1, 3-dicumyl alcohol, p-dicumyl methyl ether and 5-tert-butyl-1, 3-dicumyl methyl ether;

the coinitiator is Lewis acid;

the reaction medium is alkane and/or halogenated hydrocarbon; the alkane is selected from at least one of pentane, hexane, heptane, octane, cyclohexane and methylcyclohexane; the halogenated hydrocarbon is selected from at least one of methyl chloride, dichloromethane, trichloromethane, difluoromethane, trifluoromethane, dichloroethane, tetrafluoroethane, pentafluoroethane, hexafluoropropane, trifluoropropane, tetrafluoropropane and hexafluorobenzene.

8. The process according to claim 7, wherein the protic acid is selected from HCl and H₂SO₄And C₁-C₁₃At least one of the organic carboxylic acid compounds (3).

9. The method according to claim 8, wherein C is₁-C₁₃The organic carboxylic acid compound (2) is at least one selected from the group consisting of formic acid, acetic acid, propionic acid, n-butyric acid, 3-dimethylbutyric acid, 2-dimethylbutyric acid, n-valeric acid, hexylvaleric acid, pivalic acid, 2-propylvaleric acid, 3-methylvaleric acid, n-hexanoic acid, isocaproic acid, cyclohexanoic acid, 2-ethylhexanoic acid, n-heptanoic acid, 2-methylheptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid, benzoic acid, phenylacetic acid, chloroacetic acid, dichloroacetic acid and trichloroacetic acid.

10. The method according to claim 7, wherein the phenol is at least one selected from the group consisting of phenol, o-cresol, and p-cresol.

11. The process according to claim 7, wherein the tertiary alkanol is tert-butanol and/or 2,4, 4-trimethyl-2-hydroxypentane, and the tertiary alkaryl alcohol is cumyl alcohol and/or C₁～C₄Alkyl substituted cumyl alcohol.

12. The method according to claim 7, wherein the tertiary alkyl chloride is t-butyl chloride and/or 2,4, 4-trimethyl-2-chloropentane, and the tertiary alkyl aryl chloride is cumyl chloride and/or C₁～C₄Alkyl substituted cumyl chloride.

13. The process of claim 7, wherein the tertiary alkyl ether is methyl tert-butyl ether and the tertiary alkyl aryl ether is cumyl methyl ether and/or C₁～C₄Alkyl substituted cumyl methyl ether.

14. The method according to claim 7, wherein the tertiary alkyl ester is at least one selected from the group consisting of tert-butyl acetate, tert-butyl acetate (2,4, 4-trimethyl-2-hydroxypentyl) acetate, tert-butyl monochloroacetate, 2,4, 4-trimethyl-2-hydroxypentyl monochloroacetate, tert-butyl dichloroacetate, 2,4, 4-trimethyl-2-hydroxypentyl dichloroacetate, tert-butyl trichloroacetate and (2,4, 4-trimethyl-2-hydroxypentyl) trichloroacetate, and the tert-alkylaryl ester is selected from the group consisting of cumyl acetate, cumyl monochloroacetate, cumyl dichloroacetate, cumyl trichloroacetate, C-trimethyl-2-hydroxypentyl acetate₁～C₄Alkyl-substituted cumyl acetate, C₁～C₄Alkyl-substituted cumyl monochloroacetate, C₁～C₄Alkyl-substituted cumyl dichloroacetate and C₁～C₄At least one alkyl-substituted cumyl trichloroacetate.

15. The method according to claim 7, wherein the polyfunctional initiator is at least one selected from the group consisting of diphenyltetracumyl chloride, 1, 4-bis (2-chloro-2-propyl) benzene, 5-tert-butyl-1, 3-bis (2-chloro-2-propyl) benzene, p-dicumyl methyl ether, p-dicumyl acetate, 5-tert-butyl-1, 3-bis (1-acyloxy-1-methylethyl) benzene and 5-tert-butyl-1, 3-bis (1-methoxy-1-methylethyl) benzene.

16. The method according to claim 7, wherein the co-initiator is at least one selected from the group consisting of halides, alkyl halides and alkoxy halides of boron, aluminum, titanium, zinc, tin, iron.

17. The method of claim 16, wherein the co-initiator is at least one selected from the group consisting of boron trifluoride, titanium tetrachloride, tin tetrachloride, ferric trichloride, boron trichloride, aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, isobutylaluminum dichloride and diisobutylaluminum monochloride.

18. The method of claim 17, wherein the co-initiator is at least one selected from the group consisting of titanium tetrachloride, tin tetrachloride, ferric trichloride, boron trichloride, aluminum trichloride, and ethyl aluminum dichloride.

19. The preparation method according to any one of claims 5 to 18, wherein in the sequential active cation copolymerization reaction process, the total monomer concentration in the reaction system is 0.5-2.5 mol/L; the initiator is a coinitiator, and the mol ratio of isobutene is 1 (1-18) to 60-980; the conditions of the sequential active cation copolymerization reaction comprise that the temperature is-60 to-100 ℃, and the time is 0.1 to 2 hours;

in step S2, the bromination/chlorination reaction is performed in the presence of a bromination/chlorination initiator selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate; the bromination/chlorination reaction conditions comprise that the molar ratio of the structural unit of p-methylstyrene to the bromine element/chlorine element is (0.40-3): 1, the temperature is 50-150 ℃, and the time is 0.5-2.5 h.

20. The method according to claim 19, wherein the total monomer concentration is 0.7 to 2.0 mol/L.

21. The method according to claim 20, wherein the total monomer concentration is 0.9 to 1.6 mol/L.

22. The method of claim 19, wherein the molar ratio of the initiator, the co-initiator and the isobutylene is 1 (1-16) to (70-950).

23. The method as set forth in claim 22, wherein the molar ratio of the initiator, the co-initiator and the isobutylene is 1 (1-14) to (80-920).

24. The method of claim 19, wherein the conditions of the sequential living cationic copolymerization reaction include a temperature of-65 to-95 ℃ and a time of 0.3 to 1.5 hours.

25. The method of claim 24, wherein the conditions of the sequential living cationic copolymerization reaction include a temperature of-70 to-90 ℃ and a time of 0.4 to 1.0 hour.

26. The method of claim 19, wherein the bromination/chlorination initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and cumene hydroperoxide.

27. The method of claim 26, wherein the bromination/chlorination initiator is azobisisobutyronitrile and/or azobisisoheptonitrile.

28. The preparation method according to claim 19, wherein the bromination/chlorination reaction conditions comprise a molar ratio of p-methylstyrene structural units to bromine/chlorine (0.45-2.5): 1, a temperature of 60-120 ℃ and a time of 0.8-2.0 h.

29. The method according to claim 28, wherein the bromination/chlorination reaction is carried out under conditions including a molar ratio of p-methylstyrene structural units to bromine/chlorine (0.48-2.0): 1, a temperature of 70-100 ℃ and a time of 1.0-1.5 hours.

30. The method according to any one of claims 5 to 18, wherein in step S3, the nitrogen/phosphonium ion functionalization is performed by a solution method, and the step of the solution method comprises: dissolving the brominated/chlorinated block copolymer in a solvent, and adding a nitrogen onium ionization reagent and/or a phosphonium ionization reagent for ionization reaction to obtain a brominated/chlorinated nitrogen onium/phosphonium ion salt substituted styrene block copolymer; alternatively, the nitrogen/phosphonium ion functionalization is by a melt process, and the steps of the melt process comprise: melt blending the brominated/chlorinated block copolymer, a nitrogen onium ionizing reagent and/or a phosphonium ionizing reagent and an oxygen-containing nitrogen-containing additive to obtain a brominated/chlorinated nitrogen onium/phosphonium ion salt substituted styrene block copolymer;

when the nitrogen onium ion functionalization/phosphorus onium ion functionalization mode is a solution method, the concentration of the brominated/chlorinated block copolymer in a reaction system is 10-200 g/L; the molar ratio of benzyl bromide/benzyl chloride to a nitrogen onium ionizing reagent and/or a phosphorus onium ionizing reagent in the brominated/chlorinated block copolymer is (1-5): 1; the ionization reaction conditions comprise that the temperature is 0-95 ℃ and the time is 0.1-72 h;

when the nitrogen onium ion functionalization/phosphorus onium ion functionalization mode is a melting method, the conditions of the melt blending reaction comprise that the temperature is 100-240 ℃ and the time is 1-18 min;

the nitrogen onium ionizing agent has a structure represented by formula (6), and the phosphorus onium ionizing agent has a structure represented by formula (7):

wherein R is₁～R₇Each independently is H, C₁～C₂₀Alkyl or C₆～C₂₀Aryl group of (1).

31. The method according to claim 30, wherein when the azonium ion-functionalized/phosphonium ion-functionalized method is a solution method, the concentration of the brominated/chlorinated block copolymer in the reaction system is 15 to 100 g/L; the molar ratio of benzyl bromide/benzyl chloride to a nitrogen onium ionizing reagent and/or a phosphorus onium ionizing reagent in the brominated/chlorinated block copolymer is (1-4): 1; the conditions of the ionization reaction comprise that the temperature is 10-90 ℃ and the time is 0.5-48 h.

32. The method according to claim 31, wherein when the azonium ion-functionalized/phosphonium ion-functionalized method is a solution method, the concentration of the brominated/chlorinated block copolymer in the reaction system is 20 to 70 g/L; the molar ratio of benzyl bromide/benzyl chloride to a nitrogen onium ionizing reagent and/or a phosphorus onium ionizing reagent in the brominated/chlorinated block copolymer is (1-3): 1; the ionization reaction conditions comprise that the temperature is 25-80 ℃ and the time is 1-24 h.

33. The method of claim 30, wherein when the azonium ion-functionalized/phosphonium ion-functionalized method is a melt method, the melt blending reaction conditions include a temperature of 120 to 230 ℃ and a time of 2 to 15 min.

34. The method of claim 33, wherein when the azonium ion-functionalized/phosphonium ion-functionalized method is a melt method, the melt blending reaction conditions include a temperature of 130 to 220 ℃ and a time of 3 to 10 min.

35. The method of claim 30, wherein the step of preparing the composition comprisesIn that R is₁～R₇Each independently is C₁～C₁₅Alkyl or C₆～C₁₅Aryl group of (1).

36. The method of claim 35, wherein R is₁～R₇Each independently is C₁～C₁₀Alkyl of (C)₆～C₁₀Phenyl or alkyl substituted phenyl.

37. The method of claim 30, wherein the azonium ionizing agent is at least one selected from the group consisting of imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, N-benzylimidazole, phenylimidazole, 1-ethylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 1, 2-dimethylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2, 4-diphenylimidazole.

38. The method of claim 37, wherein the azonium ionizing agent is at least one selected from the group consisting of imidazole, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, N-benzylimidazole, and phenylimidazole.

39. The method of claim 30, wherein the azonium ionizing agent is at least one selected from the group consisting of imidazole, N-methylimidazole, N-butylimidazole, and N-benzylimidazole.

40. The method according to claim 30, wherein the phosphonium ionizing agent is at least one selected from the group consisting of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triisobutylphosphine, tri-t-butylphosphine, triphenylphosphine, triisopropylphosphine, diphenylmethylphosphine, diphenylpropylphosphine, diphenylisobutylphosphine, diphenyl-n-butylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, and dibutylphenylphosphine.

41. The method according to claim 40, wherein the phosphonium ionizing agent is at least one selected from the group consisting of tripropylphosphine, triisopropylphosphine, triisobutylphosphine, tri-t-butylphosphine, triphenylphosphine, and diphenylmethylphosphine.

42. The method of claim 30, wherein the oxygen-containing and nitrogen-containing additive is selected from the group consisting of 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl- α -aniline, 3-hydroxybutyraldehyde- α -naphthylamine, 4-octyldiphenylamine, N-diphenylethylenediamine, p-diaminodiphenylamine, 4' -bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer,2, 6-di-tert-butyl-4-methylphenol, pentaerythritol ester, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl ester, and mixtures thereof, Styrenated phenol, 2' -thiobis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-methyl-. alpha. -methylcyclohexyl) phenol, tris (3, 5-di-tert-butyl-4-hydroxybenzyl isocyanurate), nickel dithiocarbamate, diethyl 3,5' -di-tert-butyl-4-hydroxybenzyl phosphate, cyclohexyl-N ' -phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, 2' -methylenebis (4-ethyl-6-tert-butylphenol), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, di-tert-butyl-4-hydroxy-phenyl-ethyl-phenyl-methyl-2, 4, 6-methyl-phenyl-2, 5-methyl-4, 6-tri (3, di-tert-butyl-4-hydroxybenzyl) benzene, di-butyl-4-hydroxy-methyl-phenyl-ethyl-3, 2' -methylene bis (4-methyl-benzyl) phenyl-4-ethyl-hydroxy-phenyl-ethyl-methyl-phenyl-2, 5-methyl-4-phenyl-ethyl-phenyl-butyl-phenyl-ethyl-phenyl-ethyl-2, 2, 5-ethyl-butyl-phenyl-ethyl-4-ethyl-phenyl-ethyl-butyl-phenyl-ethyl-butyl-ethyl-phenyl-ethyl, At least one of 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc salt, carbodiimide, and N-isopropyl-N' -phenyl-p-phenylenediamine.

43. The method of claim 42, wherein the oxygen-containing and nitrogen-containing additive is selected from the group consisting of 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, N-phenyl-alpha-aniline, 3-hydroxybutyraldehyde-alpha-naphthylamine, 4-octyldiphenylamine, N, at least one of N-diphenylethylenediamine, p-diaminodiphenylamine, 4' -bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer,2, 6-di-tert-butyl-4-methylphenol, pentaerythritol ester, and octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.

44. The method of claim 43, wherein the oxygen-containing and nitrogen-containing additive is at least one selected from the group consisting of 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, 3-hydroxybutyraldehyde- α -naphthylamine, 4' bis (a, a-dimethylbenzyl) diphenylamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, pentaerythritol ester, and octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.

45. The preparation method according to any one of claims 5 to 18, wherein in step S3, the amine group functionalization is performed by subjecting the brominated/chlorinated block copolymer to amination reaction in the presence of an amination reagent and a reaction medium, then adding hydrazine hydrate to perform reduction reaction, adding an alkane solvent after the reaction is finished, stirring for 20-40 min, adding water, transferring to a separating funnel for extraction, mixing an upper layer substance with a poor solvent and flocculating and separating out, washing and drying the obtained precipitate to obtain the amine group functionalized styrene-based block copolymer;

the amination reagent is potassium phthalimide;

the reaction medium is a mixed solvent of tetrahydrofuran and at least one of azomethyl pyrrolidone, azoethyl pyrrolidone, azopropyl pyrrolidone and azobutyl pyrrolidone;

the amination reaction conditions comprise that the temperature is 50-120 ℃, and the time is 1-36 h;

the poor solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone.

46. The process according to claim 45, wherein the reaction medium is a mixed solvent of tetrahydrofuran and at least one of azomethylpyrrolidone, azoethylpyrrolidone and azopropylpyrrolidone.

47. The process according to claim 46, wherein the reaction medium is a mixed solvent of tetrahydrofuran and N-methylpyrrolidone.

48. The method of claim 45, wherein the amination reaction is carried out at a temperature of 60 to 110 ℃ for 2 to 30 hours.

49. The method of claim 48, wherein the amination reaction is carried out at a temperature of 70 to 100 ℃ for 3 to 24 hours.

50. The method according to claim 45, wherein the poor solvent is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, water, acetone, and methyl ethyl ketone.

51. The method according to claim 50, wherein the poor solvent is at least one selected from the group consisting of methanol, ethanol, water and methyl ethyl ketone.

52. The preparation method according to any one of claims 5 to 18, wherein in step S3, the hydroxyl group is functionalized by subjecting the brominated/chlorinated block copolymer to hydrolysis reaction in the presence of an alkaline substance and a reaction medium, adding an alkane solvent and stirring for 20 to 40min after the reaction is finished, adding water, transferring to a separating funnel for extraction, mixing an upper layer substance with a poor solvent and flocculating and separating out, washing and drying the obtained precipitate to obtain a hydroxyl-functionalized styrene-based block copolymer;

the alkaline substance is sodium hydroxide and/or potassium hydroxide;

the poor solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, butanediol, n-pentanol, isopentanol, cyclopentanol, pentaerythritol, n-hexanol, isohexanol, cyclohexanol, water, acetone, and butanone;

the hydrolysis reaction conditions comprise that the temperature is 50-150 ℃ and the time is 1-36 h.

53. The process according to claim 52, wherein the reaction medium is a mixed solvent of tetrahydrofuran and at least one of azomethylpyrrolidone, azoethylpyrrolidone and azopropylpyrrolidone.

54. The process according to claim 53, wherein the reaction medium is a mixed solvent of tetrahydrofuran and N-methylpyrrolidone.

55. The method according to claim 52, wherein the poor solvent is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, water, acetone, and methyl ethyl ketone.

56. The method according to claim 55, wherein the poor solvent is at least one selected from methanol, ethanol, water and methyl ethyl ketone.

57. The method as claimed in claim 52, wherein the hydrolysis reaction is carried out at a temperature of 60-120 ℃ for 2-30 h.

58. The method as claimed in claim 57, wherein the hydrolysis reaction is carried out at a temperature of 70-100 ℃ for 3-24 hours.