CN110229293B - Star block copolymer and preparation method thereof - Google Patents
Star block copolymer and preparation method thereof Download PDFInfo
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- CN110229293B CN110229293B CN201810178643.3A CN201810178643A CN110229293B CN 110229293 B CN110229293 B CN 110229293B CN 201810178643 A CN201810178643 A CN 201810178643A CN 110229293 B CN110229293 B CN 110229293B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
Abstract
The invention relates to the field of polymers, in particular to a star-shaped block copolymer and a preparation method thereof. The star-shaped block copolymer contains a structure providing a star center and a block polymer chain bonded with the star center; wherein the structure providing the star center is provided by a styrene-based copolymer composed of a structural unit represented by formula (1) and a structural unit represented by formula (2); the block polymer chain comprises a block A and a block B, wherein the block polymer chain is bonded with the structure providing the star center through the block A; the block A is provided by an isomonoolefin represented by formula (3), and the block B is provided by a styrenic monomer represented by formula (4). The star-shaped block copolymer provided by the invention is simple in preparation process, and the obtained star-shaped block copolymer has excellent mechanical strength.
Description
Technical Field
The invention relates to the field of polymers, in particular to a star-shaped block copolymer and a preparation method thereof.
Background
The synthesis of thermoplastic elastomers generally involves the preparation of triblock copolymers having soft blocks in the rubbery state and hard blocks in the plastic state. The plastic hard segments are typically vinyl aromatics (e.g., polystyrene), while the rubbery soft segments are typically polybutadiene or polyisoprene. The predominant styrenic thermoplastic elastomers are polystyrene-butadiene-styrene triblock copolymers (SBS). The preparation of SBS by using active anion technique is widely used in industry, but the SBS prepared by the technique has many disadvantages: polybutadiene in the soft segment structure contains double bonds with high unsaturation, resulting in poor heat resistance, weather resistance and aging resistance of SBS. Although the hydrogenation method can improve the performance of SBS and raise the thermal oxygen stability and use temperature of SBS, the hydrogenation method needs noble metal as catalyst, and the process is complicated and high in cost. In addition, hydrogenation of polybutadiene chain segments tends to form polyethylene chain segments, which lose their original elasticity.
The polystyrene-isobutylene-styrene (SIBS) synthesized by using the active cation technology overcomes the above disadvantages. The advantages of SIBS over SBS are mainly reflected in: (1) the middle rubber soft segment is a fully saturated structure of polyisobutylene, so that the SIBS has more excellent air tightness and thermal oxygen stability; (2) since the lateral methyl groups are closely arranged on both sides of the isobutylene, the SIBS has more excellent shock absorption performance.
Among them, CN1332757A discloses a preparation method of triblock copolymer including styrene/isoolefin copolymer midblock, which comprises: firstly, under the condition of carbocation polymerization, isomonoolefin and first vinyl aromatic monomer are polymerized in an active mode, then the isomonoolefin is added for polymerization, and finally, a second vinyl aromatic monomer is added for polymerization, so that a novel triblock copolymer is synthesized. The triblock copolymer and the preparation method thereof have the advantages that the block copolymer can be further halogenated, functionalized and grafted to prepare derivatives, but still have the defect of poor mechanical strength.
CN1982350A discloses a method for preparing a soft-block fully saturated block copolymer, which comprises the steps of using styrene monomer or isoolefin as a first monomer, using cheap water as an initiator and Lewis acid as a co-initiator in a polymerization system containing a solvent and an additive to control cationic polymerization, and then adding isoolefin monomer or styrene second monomer containing the additive to perform second-stage polymerization to obtain a two-block copolymer, or adding the first monomer to perform polymerization to obtain a three-block copolymer SIBS when the second-stage reaction is finished. The triblock copolymer and the preparation method thereof have the advantages of low price and low cost of the initiator, but still have the defects of low polymerization rate, complicated steps and low block efficiency.
US5428111 discloses a process for preparing a segmented copolymer of polyisobutylene, which comprises the steps of initiating isobutylene to perform living cationic polymerization to generate polyisobutylene with a predetermined molecular weight, adding a capping reagent to perform a capping reaction to form a relatively stable cationic active center, and then adding styrene to continue polymerization in a composite solvent by using bifunctional organic tertiary alkyl chloride as an initiator, titanium tetrachloride as a coinitiator and sterically hindered pyridine as a proton trapping agent. The preparation method has the advantages of high block efficiency, but still has the defects of long polymerization time and complicated steps.
Disclosure of Invention
The invention aims to provide a novel SIBS with higher mechanical strength, namely a star-shaped block copolymer and a preparation method thereof.
In order to achieve the above object, one aspect of the present invention provides a star block copolymer comprising a structure providing a star center and a block polymer chain bonded to the star center; wherein the structure providing the star center is provided by a styrene copolymer, and the styrene copolymer is composed of a structural unit shown in a formula (1) and a structural unit shown in a formula (2); the block polymer chain comprises a block A and a block B, wherein the block polymer chain is bonded with the structure providing the star center through the block A; the block A is provided by an isomonoolefin represented by formula (3), and the block B is provided by a styrenic monomer represented by formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from the group consisting of H, C1-C8 alkyl and C1-C8 alkoxy; x is halogen; r is3And R4Each independently selected from C1-C5 alkyl.
In a second aspect, the present invention provides a method for preparing a star-shaped block copolymer, the method comprising:
(1) in the presence of Lewis acid, nucleophilic reagent and proton trapping agent, in organic solvent, styrene copolymer providing carbocation and isomonoolefin are first cationic polymerized to obtain star-shaped polyisomonoolefin polymerization system with reactive end;
(2) carrying out a second cationic polymerization reaction on the polymerization system obtained in the step (1) and a styrene monomer to obtain a star-shaped block copolymer; the star-shaped center structure of the star-shaped block copolymer is provided by the styrene copolymer, and the block polymer chain bonded with the star-shaped center is provided by isomonoolefin and styrene monomer;
wherein the styrene copolymer is composed of a structural unit represented by formula (1) and a structural unit represented by formula (2);
the isomonoolefin is a compound shown in a formula (3), and the styrene monomer is a compound shown in a formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from the group consisting of H, C1-C8 alkyl and C1-C8 alkoxy; x is halogen; r3And R4Each independently selected from C1-C5 alkyl.
In a third aspect, the present invention provides a radial block copolymer prepared by the above method.
The star-shaped block copolymer provided by the invention is simple in preparation process, and the obtained star-shaped block copolymer has higher molecular weight and excellent mechanical strength.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a star-shaped block copolymer, which contains a structure for providing a star center and a block polymer chain bonded with the star center; wherein the structure providing the star center is provided by a styrene copolymer, and the styrene copolymer is composed of a structural unit shown in a formula (1) and a structural unit shown in a formula (2); the block polymer chain comprises a block A and a block B, wherein the block polymer chain is bonded with the structure providing the star center through the block A; the block A is provided by an isomonoolefin represented by formula (3), and the block B is provided by a styrenic monomer represented by formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from the group consisting of H, C1-C8 alkyl and C1-C8 alkoxy; x is halogen; r3And R4Each independently selected from C1-C5 alkyl.
According to the present invention, the star-type block copolymer means that a star-type central structure having a plurality of active sites is linked to a plurality of block polymer chains, so that the plurality of block polymer chains form arms of the star-type block copolymer, thereby forming a star-type structured macromolecule. Preferably, in the star-shaped block copolymer, the content of the structure providing the star-shaped center is 1 to 10% by weight, and the content of the block polymer chain is 90 to 99% by weight. More preferably, in the star-shaped block copolymer, the content of the structure providing the star-shaped center is 1 to 7% by weight, and the content of the block polymer chain is 93 to 99% by weight.
According to the present invention, the alkyl group of C1 to C8 includes a linear alkyl group of C1 to C8 and a branched alkyl group of C3 to C8, and specific examples thereof may include, but are not limited to: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2 dimethylpropyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4 methylpentyl group, 2, 3-dimethylbutyl group, 2-dimethylbutyl group, 3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2-dimethylpentyl group, 2, 3-dimethylpentyl group, 2, 4-dimethylpentyl group, 3-dimethylpentyl group, 3, 4-dimethylpentyl group, 4-dimethylpentyl group, 2-ethylpentyl group, 3-pentyll group, 2-dimethylpentyl group, N-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-dimethylhexyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 3-dimethylhexyl, 3, 4-dimethylhexyl, 3, 5-dimethylhexyl, 4-dimethylhexyl, 4, 5-dimethylhexyl, 5-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-propylpentyl and 2-isopropylpentyl.
Specific examples of the C1-C5 alkyl group and the C1-C4 alkyl group can be appropriately selected from the same range of the number of carbon atoms as those exemplified above for the C1-C8 alkyl group.
According to the invention, preferably each R1And R2Each independently selected from H and C1-C4 alkyl; x is F, Cl, Br or I; r3And R4Each independently selected from C1-C4 alkyl.
More preferably, each R1And R2Each independently selected from H, methyl, ethyl and n-propyl; x is Cl or Br; r3And R4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
According to the invention, the structure providing the star center is provided by the styrene copolymer which contains a benzyl structure with halogen, so that the carbocation active sites are easily provided, and a plurality of carbocation active sites are formed on the chain of the styrene copolymer to be convenient for connecting with the block polymer chain.
Among them, in a preferred embodiment of the present invention, in the structural unit represented by the formula (1), R is1Is H; in the structural unit represented by the formula (2), R1And R2Are all H, and X is Cl. That is, the structural unit represented by the formula (1) is provided by styrene, and the structural unit represented by the formula (2) is provided by p-vinylbenzyl chloride.
According to the present invention, it is preferable that the styrene-based copolymer has a molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) of 1: 0.01 to 0.3, preferably 1: 0.015 to 0.1, more preferably 1: 0.03-0.08.
According to the present invention, it is preferred that the styrene-based copolymer has a weight average molecular weight of 20,000-150,000g/mol, preferably 30,000-130,000g/mol, more preferably 50,000-100,000g/mol, still more preferably 60,000-80,000 g/mol; the molecular weight distribution index is 1 to 3, preferably 1.5 to 2.5.
According to the present invention, the styrenic copolymer may be prepared by a method conventional in the art, for example, the method for preparing the styrenic copolymer may comprise:
carrying out free radical polymerization reaction on a monomer shown in a formula (1-a) and a monomer shown in a formula (2-a) in an aqueous solvent in the presence of a pore-forming agent and a free radical initiator; soaking the product of the polymerization reaction in an acid solution, filtering and drying to obtain the styrene copolymer of the invention, wherein:
formula (1-a)
Formula (2-a)
In the above formula (1-a) and formula (2-a), the selection of each group is as described above, and the present invention is not described herein again.
Wherein the amount of the monomer represented by the formula (1-a) and the monomer represented by the formula (2-a) may be selected depending on the desired styrenic copolymer, and for example, the molar ratio of the amount of the monomer represented by the formula (1-a) to the amount of the monomer represented by the formula (2-a) is 1: 0.01 to 0.3, preferably 1: 0.015 to 0.1, more preferably 1: 0.03-0.08.
Wherein, the pore-forming agent can be one or more of magnesium carbonate, magnesium oxide, calcium carbonate, potassium carbonate and the like; by adopting the pore-foaming agent, the styrene copolymer particles with porous structures can be obtained after the products of the polymerization reaction are treated by the subsequent acid solution. The amount of the porogen may vary within a wide range, and preferably, the amount of the porogen is 2 to 10 parts by weight with respect to 100 parts by weight of the styrenic copolymer.
Wherein, the free radical initiator can be one or more of dibenzoyl peroxide, dicumyl peroxide, benzoyl peroxide, di-o-methylbenzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile and the like; preferably, the radical initiator is used in an amount of 0.2 to 3 mol%, preferably 0.8 to 1.5 mol%, based on the monomer represented by the above formula (1-a).
The aqueous solvent may be water alone or may contain other solvents that do not affect the radical polymerization reaction, and is preferably water. The amount of the aqueous solvent to be used may vary within a wide range, and is preferably 40 to 200mL relative to 100mmol of the monomer represented by the formula (1-a).
Wherein, the conditions of the free radical polymerization reaction preferably comprise: firstly, reacting for 6-10h at 70-90 ℃; then reacting for 1-3h at 90-100 ℃.
The acid solution may be, for example, a dilute solution of hydrochloric acid, sulfuric acid, nitric acid, etc., and the concentration thereof may be, for example, 0.5 to 5 mol/L.
According to the present invention, the block polymer chain bonded to the star center as the arm of the star block copolymer of the present invention is actually a block copolymer structure comprising a block A and a block B, and the end of the block polymer chain connected to the structure of the star center is a block A end, that is, a structure forming a star center structure-block A-block B.
According to the invention, the block A is provided by an isomonoolefin represented by (3), wherein specific examples of the isomonoolefin may include, for example: one or more of 2-methyl-1-propene (i.e., isobutylene), 2-methyl-1-butene, 2, 3-dimethyl-1-butene, 2-methyl-1-pentene, 2, 3-dimethyl-1-pentene, 2, 4-dimethyl-1-pentene, 2-methyl-1-hexene, 2, 3-dimethyl-1-hexene, 2, 4-dimethyl-1-hexene, 2, 5-dimethyl-1-hexene, 2,4, 4-trimethyl-1-pentene and the like, and preferably isobutylene.
According to the present invention, the block B is provided by a styrenic monomer represented by formula (4), and specific examples of the styrenic monomer may include, for example: one or more of styrene, p-methylstyrene, o-methylstyrene, and m-methylstyrene, etc., preferably styrene.
According to the present invention, it is preferable that the molar ratio of the structural unit provided by the isomonoolefin represented by the formula (3) to the structural unit provided by the styrenic monomer represented by the formula (4) in the block polymer chain is 1 to 6: 1, preferably 3 to 5: 1.
according to the present invention, preferably, the block polymer chain has a weight average molecular weight of 1,000-10,000g/mol, preferably 1,500-9,000g/mol, more preferably 3,000-8,500g/mol, still more preferably 5,000-8,000g/mol, more preferably 6,000-8,000 g/mol.
In a preferred embodiment of the present invention, the block polymer chain is composed substantially of the block A and the block B, and of course, a random copolymerization portion of the structural unit provided by the isomonoolefin represented by the formula (3) and the structural unit provided by the styrenic monomer represented by the formula (4) may be present in a small amount at the junction of the block A and the block B in the block polymer chain, or the structural unit provided by the isomonoolefin represented by the formula (3) may be present in a small amount in the block B, but these cases are included in the scope of the present invention.
According to the present invention, it is preferred that the weight average molecular weight of the star block copolymer is 100,000-2,000,000g/mol, preferably 300,000-1,000,000g/mol, more preferably 350,000-980,000g/mol, still more preferably 550,000-980,000g/mol, more preferably 700,000-980,000g/mol, for example 800,000-960,000 g/mol; the molecular weight distribution index is 1.5-3.
In a second aspect, the present invention provides a method for preparing a star-shaped block copolymer, the method comprising:
(1) in the presence of Lewis acid, nucleophilic reagent and proton trapping agent, in organic solvent, styrene copolymer providing carbocation and isomonoolefin are first cationic polymerized to obtain star-shaped polyisomonoolefin polymerization system with reactive end;
(2) carrying out a second cationic polymerization reaction on the polymerization system obtained in the step (1) and a styrene monomer to obtain a star-shaped block copolymer; the star-shaped center structure of the star-shaped block copolymer is provided by the styrene copolymer, and the block polymer chain bonded with the star-shaped center is provided by isomonoolefin and styrene monomer;
wherein the styrene copolymer is composed of a structural unit represented by formula (1) and a structural unit represented by formula (2);
the isomonoolefin is a compound shown in a formula (3), and the styrene monomer is a compound shown in a formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from the group consisting of H, C1-C8 alkyl and C1-C8 alkoxy; x is halogen; r3And R4Each independently selected from C1-C5 alkyl.
According to the present invention, the styrenic copolymer, the isomonoolefin represented by formula (3), and the styrenic monomer represented by formula (4) are as described above, and the present invention will not be described in detail herein.
According to the present invention, the styrenic copolymer is preferably provided in the form of a solution thereof, and the concentration of the solution containing the styrenic copolymer may be, for example, 1 to 10 mg/mL. The solvent for the solution containing the styrenic copolymer may be one or more of a halogenated alkane solvent and a non-halogenated alkane solvent described hereinafter.
According to the present invention, the amount of the styrenic copolymer, the isomonoolefin and the styrenic monomer may be appropriately selected depending on the content of each structure in the desired star-block copolymer, and preferably, the styrenic copolymer is used in an amount of 1 to 10% by weight and the isomonoolefin and the styrenic monomer are used in an amount of 90 to 99% by weight, based on the total weight of the styrenic copolymer, the isomonoolefin and the styrenic monomer. More preferably, the styrenic copolymer is used in an amount of 1 to 7 wt.% and the isomonoolefin and styrenic monomer are used in an amount of 93 to 99 wt.%, based on the total weight of the styrenic copolymer, isomonoolefin, and styrenic monomer.
According to the present invention, the amount ratio of the isomonoolefin to the styrene monomer may be appropriately selected depending on the ratio of the structural unit required for the block polymer chain as the polymer arm in the star block copolymer, and preferably, the molar ratio of the isomonoolefin to the styrene monomer is 1 to 6: 1, preferably 3 to 5: 1.
according to the invention, in step (1), the styrene copolymer can form carbocations with a plurality of reactive sites under the reaction system provided in step (1) so as to perform a first cationic polymerization reaction with isomonoolefin, so that polyisomonoolefin with reactive tail end, namely block A, is connected on the styrene copolymer at a certain ratio, thereby obtaining a star-shaped polyisomonoolefin polymerization system.
According to the present invention, preferably, the lewis acid is one or more of titanium tetrachloride, boron trifluoride, ethyl aluminum dichloride, aluminum trichloride, zinc chloride, tin dichloride, ferric trichloride, and antimony pentafluoride, preferably titanium tetrachloride.
The amount of the Lewis acid used may vary within wide limits and is preferably from 1 to 10 mol%, preferably from 1 to 5 mol%, based on the molar sum of the isomonoolefin and the styrenic monomer.
According to the present invention, preferably, the nucleophilic reagent is one or more of N, N-dimethylacetamide, dimethylsulfoxide, triethylamine, acetone, methanol, ethanol and tert-butanol, preferably one or more of N, N-dimethylacetamide, dimethylsulfoxide and triethylamine.
The amount of the nucleophile can vary within wide limits and is preferably from 0.1 to 1 mol%, preferably from 0.2 to 0.5 mol%, based on the molar sum of the isomonoolefin and the styrenic monomer.
According to the invention, the nucleophile may be provided as a pure substance or in another form, preferably the nucleophile is provided in the form of a solution thereof, the concentration of the solution containing the nucleophile being 0.01 to 5mmol/L, preferably 0.1 to 0.5 mmol/L. The solvent of the nucleophile-containing solution may be one or more of the haloalkane solvents and non-haloalkane solvents described hereinafter.
According to the present invention, preferably, the proton scavenger is one or more of 2, 6-di-tert-butylpyridine, 2, 6-di-tert-butyl-4-methylpyridine, pyridine, and tetramethylpiperidine.
The amount of said proton scavenger may vary within wide limits and is preferably from 0.02 to 0.2 mol%, based on the molar sum of the isomonoolefin and the styrenic monomer.
According to the invention, the proton scavenger may be provided as a pure substance or in another form, preferably in the form of a solution thereof, the concentration of the solution containing the proton scavenger being 0.01 to 5mmol/L, preferably 0.1 to 0.5 mmol/L. The solvent of the solution containing the proton scavenger may be one or more of a halogenated alkane solvent and a non-halogenated alkane solvent described below.
According to the present invention, the proton scavenger may be introduced into the reaction system of the present invention in two parts, a first part of the proton scavenger being introduced during step (1) to participate in the first cationic polymerization reaction, and a second part of the proton scavenger being introduced during step (2) to participate in the second cationic polymerization reaction; wherein the weight ratio of the first portion of proton-capturing agent to the second portion of proton-capturing agent is preferably 2 to 5: 1.
according to the present invention, in step (1), the organic solvent may be one or more of a non-halogenated alkane solvent and a halogenated alkane solvent, and preferably, in step (1), the organic solvent is composed of a first organic solvent and a second organic solvent, the first organic solvent is a non-halogenated alkane solvent, and the second organic solvent is a halogenated alkane solvent. More preferably, the volume ratio of the first organic solvent to the second organic solvent is 100: 10-600, preferably 100: 50-300.
Specific examples of the non-halogenated alkane solvent may include, but are not limited to: propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2-ethylpentane, 3-ethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2, 3-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3-ethylhexane, 2, 3-trimethylpentane, 2,3, 3-trimethylpentane, 2,4, 4-trimethylpentane, 2-methyl-3-ethylpentane, 2-methylpentane, 3-methylpentane, 2-methyl-3-ethylpentane, N-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2, 3-dimethylheptane, 2, 4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3, 4-trimethylhexane, 2,3, 5-trimethylhexane, 2,4, 5-trimethylhexane, 2, 3-trimethylhexane, 2, 4-trimethylhexane, 2, 5-trimethylhexane, 2,3, 3-trimethylhexane, 2,4, 4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 4-methylhexane, 2-dimethylheptane, 2, 3-dimethylheptane, 4-dimethylheptane, 2, 3-dimethylheptane, 2, 4-trimethylhexane, 2, 3-methyl-3-ethylhexane, 4-trimethylhexane, 2-methyl-ethyl-2, 2-ethyl-hexane, 2-ethyl-2, 2-ethyl-hexane, 2-ethyl-hexane, 2, 3-ethyl-3-ethyl-3, 2, 3-ethyl-3, 2, 3-ethyl-3, 3-ethyl-3-4-ethyl-n, 3, 3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane, n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2, 3-dimethyloctane, 2, 4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3, 4-trimethylheptane, 2,3, 5-trimethylheptane, 2,3, 6-trimethylheptane, 2,4, 5-trimethylheptane, 2,4, 6-trimethylheptane, 2, 3-trimethylheptane, 2,2, 4-trimethylheptane, 2, 5-trimethylheptane, 2, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3, 3-diethylhexane, 3, 4-diethylhexane, 2-methyl-3, 3-diethylpentane, 1, 2-diethylcyclohexane, 1-diethylcyclohexane, 2-dimethylheptane, 2-methyl-3, 3-diethylheptane, 2-methyl-4-ethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 3-diethylheptane, 3-diethylhexane, 3-diethylheptane, 2-ethylheptane, 6-trimethylheptane, 2-trimethylheptane, 3-ethylheptane, 4-ethylheptane, etc, One or more of 1, 3-diethylcyclohexane, 1, 4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane and tetramethylcyclohexane.
Specific examples of the haloalkane-based solvent may include, but are not limited to: monochloromethane, dichloromethane, trichloromethane, carbon tetrachloride, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, hexafluorocarbon, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachlorocarbon, monofluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, octafluoropropane, monochloropropane, dichloropropane, one or more of trichloropropane, tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane, octachloropropane, monofluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, decafluorobutane, monochlorobutane, dichlorobutane, trichlorobutane, tetrachlorobutane, pentachlorobutane, hexachlorobutane, heptachlorobutane, octachlorobutane, nonachlorobutane, and decachlorobutane.
In a preferred embodiment of the present invention, the first organic solvent is n-hexane and the second organic solvent is monochloromethane.
According to the invention, the amount of the organic solvent can vary within a wide range, and preferably, in step (1), the amount of the organic solvent is 100-1000mL, preferably 200-800mL, and more preferably 300-600mL, relative to 1mol of the isomonoolefin.
According to the present invention, it is preferable that the first cationic polymerization reaction in the step (1) is carried out so that the conversion of isomonoolefin is 90% or more, preferably 95 to 100%.
According to the present invention, preferably, in the step (1), the conditions of the first cationic polymerization reaction include: the temperature is-100 ℃ to 20 ℃, preferably-100 ℃ to 0 ℃; the time is 50-120min, preferably 60-100 min.
According to the present invention, in the step (1), the isomonoolefin may be first mixed with the organic solvent, and then the nucleophilic agent and the proton scavenger may be added and mixed (the mixing condition includes a temperature of-100 ℃ to 20 ℃, preferably-100 ℃ to 0 ℃, for a time of 5 to 20min), and the lewis acid may be added and the first cationic polymerization may be performed.
According to the present invention, in the step (2), the polymerization system obtained in the step (1) still contains an initiation system such as Lewis acid, nucleophilic agent and proton scavenger, and under the continued initiation of such an initiation system, the styrenic monomer is introduced so that the styrenic monomer is bonded to the living end of the block A to form the block B, thereby forming a block polymer chain having the block A and the block B.
According to the present invention, preferably, in step (2), the styrenic monomer is provided in the form of a solvent thereof, and the solution containing the styrenic monomer has a concentration of 0.1 to 5mol/L, preferably 1 to 3 mol/L. Wherein a second portion of the proton scavenger described hereinabove is introduced into the solution comprising styrenic monomer.
The solvent in the solution containing the styrenic monomer may be suitably selected from the organic solvents described hereinabove, and the present invention will not be described in detail herein.
According to the present invention, preferably, the conditions of the second cationic polymerization reaction include: the temperature is-100 ℃ to 20 ℃, preferably-100 ℃ to 0 ℃; the time is 50-120min, preferably 60-100 min.
According to the present invention, in order to be able to maintain the initiating activity of the initiating system of the process of the present invention, the above step (1) and step (2) may be carried out in an inert atmosphere, which may be provided by one or more of nitrogen, helium, neon, argon, and the like.
According to the present invention, the method may further comprise adding a polymerization terminator (e.g., alcohol) to the mixture obtained by the polymerization after completion of the polymerization to terminate the polymerization reaction. The type and amount of the polymerization terminator in the present invention are not particularly limited, and may be selected conventionally in the art, so as to terminate the polymerization reaction, and are not described herein again.
According to the invention, in order to extract the star-shaped block copolymer from the terminated product, the terminated product is poured into water, unreacted monomers and solvent are removed at 90-100 ℃, and then the star-shaped block copolymer is obtained after water washing and drying.
In a third aspect, the present invention provides a radial block copolymer prepared by the above method.
The star block copolymer provided by the third aspect of the present invention is obtained by the above-mentioned method, and such a star block copolymer may have the properties associated with the star block copolymer described hereinabove in the present invention.
The star-shaped block copolymer provided by the invention has higher mechanical property.
The present invention will be described in detail below by way of examples.
Preparation example 1
This preparation example is intended to illustrate the preparation of a carbonium ion-providing styrenic copolymer of the present invention.
400mL of distilled water and 4g of magnesium carbonate powder are stirred and mixed, then 700mmol of styrene, 28mmol of 4-vinylbenzyl chloride and 6.6mmol of dibenzoyl peroxide are added, stirring is continued for 30min, the temperature is raised to 85 ℃, and the constant temperature reaction is carried out for 9 h. Then opening the bottle mouth, heating to 98 ℃ and continuously heating for 2h, and then cooling. Filtering the obtained product to obtain polymer particles, soaking the polymer particles in 1mol/L dilute hydrochloric acid aqueous solution for 30min, filtering, washing with water to neutrality, and vacuum drying at 60 ℃ to constant weight to obtain styrene copolymer P1, wherein the styrene copolymer P1 has a structural unit (R) shown in formula (1)1Is H) and a structural unit (R) represented by the formula (2)1And R2All H, X Cl) in a molar ratio of 1: 0.037, weight average molecular weight 64,600g/mol, molecular weight distribution index 1.68.
Preparation example 2
This preparation example is intended to illustrate the preparation of a carbonium ion-providing styrenic copolymer of the present invention.
400mL of distilled water and 4g of magnesium carbonate powder are stirred and mixed, then 700mmol of styrene, 56mmol of 4-vinylbenzyl chloride and 7.4mmol of dibenzoyl peroxide are added, stirring is continued for 30min, the temperature is raised to 85 ℃, and the constant temperature reaction is carried out for 9 h. Then opening the bottle mouth, heating to 98 ℃ and continuously heating for 2h, and then cooling. Filtering the obtained product to obtain polymer particles, soaking in 1mol/L dilute hydrochloric acid water solution for 30min, filtering, washing with water to neutrality, and vacuum drying at 60 deg.CDrying to constant weight, thereby obtaining a styrenic copolymer P1 comprising the structural unit (R) represented by the formula (1)1Is H) and a structural unit (R) represented by the formula (2)1And R2All H, X Cl) in a molar ratio of 1: 0.068, weight average molecular weight 76,500g/mol, molecular weight distribution index 1.70.
Preparation example 3
This preparation example is intended to illustrate the preparation of a carbonium ion-providing styrenic copolymer of the present invention.
400mL of distilled water and 4g of magnesium carbonate powder are stirred and mixed, 700mmol of styrene, 14mmol of 4-vinylbenzyl chloride and 15.7mmol of dibenzoyl peroxide are added, stirring is continued for 30min, and then the temperature is raised to 85 ℃ for constant-temperature reaction for 9 h. Then opening the bottle mouth, heating to 98 ℃ and continuously heating for 2h, and then cooling. Filtering the obtained product to obtain polymer particles, soaking the polymer particles in 1mol/L dilute hydrochloric acid aqueous solution for 30min, filtering, washing with water to neutrality, and vacuum drying at 60 ℃ to constant weight to obtain styrene copolymer P1, wherein the styrene copolymer P1 has a structural unit (R) shown in formula (1)1Is H) and a structural unit (R) represented by the formula (2)1And R2All H, X Cl) in a molar ratio of 1: 0.019, a weight average molecular weight of 34,500g/mol, and a molecular weight distribution index of 1.65.
Preparation example 4
This preparation example is intended to illustrate the preparation of a carbonium ion-providing styrenic copolymer of the present invention.
Stirring and mixing 400mL of distilled water and 4g of magnesium carbonate powder, adding 700mmol of styrene, 85mmol of 4-vinylbenzyl chloride and 3.3mmol of dibenzoyl peroxide, continuing stirring for 30min, heating to 85 ℃, and reacting at constant temperature for 9 h. Then opening the bottle mouth, heating to 98 ℃ and continuously heating for 2h, and then cooling. Filtering the obtained product to obtain polymer particles, soaking the polymer particles in 1mol/L dilute hydrochloric acid aqueous solution for 30min, filtering, washing with water to neutrality, and vacuum drying at 60 ℃ to constant weight to obtain styrene copolymer P1, wherein the styrene copolymer P1 has a structural unit (R) shown in formula (1)1Is H) and a structural unit (R) represented by the formula (2)1And R2All H, X Cl) in a molar ratio of 1: 0.090, weight average molecular weight 121,000g/mol, molecular weightThe cloth index was 1.86.
Example 1
This example illustrates the star block copolymers of the present invention and their preparation.
(1) 598mmol of isobutylene (about 33.5g), 190mL of N-hexane and 126mL of monochloromethane are placed in a cold bath at-80 ℃ under nitrogen protection and stirred and mixed for 20min, and then 20mL of a methylene chloride solution of styrenic copolymer P1 (the concentration of copolymer P1 is 5mg/mL), 15mL of a methylene chloride solution of N, N-dimethylacetamide (the concentration of N, N-dimethylacetamide is 0.11mmol/mL) and 4mL of a methylene chloride solution of 2, 6-di-tert-butylpyridine (the concentration of 2, 6-di-tert-butylpyridine is 0.12mmol/mL) are added and stirred and mixed for 10 min; and then 11mmol of titanium tetrachloride was added to the mixed system and the first cationic polymerization was carried out at-80 ℃ for 70min, whereby the conversion of isobutylene was 100%;
(2) preparing a styrene solution containing 2, 6-di-tert-butylpyridine to obtain a mixed solution containing 175mmol of styrene (about 18.2g), 48mL of n-hexane, 32mL of dichloromethane and 0.9mL of a dichloromethane solution of 2, 6-di-tert-butylpyridine (the concentration of 2, 6-di-tert-butylpyridine is 0.12mmol/mL), adding the styrene solution to the first cationic polymerization product obtained in step (1), and continuing to perform a second cationic polymerization at-80 ℃ for 80min, whereby the conversion of styrene is 100%.
And (3) terminating the second cationic polymerization reaction product, mixing the polymer solution obtained after termination with clean water with the same volume, removing unreacted monomers and solvents at 100 ℃, washing with water for three times, naturally drying, and putting into a vacuum oven to dry to constant weight to obtain the copolymer A1.
The weight average molecular weight of the copolymer was identified to be 960,000g/mol, and the molecular weight distribution index was 2.11; the copolymer is of a star-shaped structure and is provided with a star-shaped central structure and an isobutylene-styrene block copolymer chain connected with the star-shaped central structure, wherein the content of the star-shaped central structure is 3 wt%, the content of the block copolymer chain is 97 wt%, and the weight average molecular weight of the block copolymer chain is 7,600 g/mol; in the block copolymer chain, the molar ratio of the structural units of isobutylene and styrene was 3.4: 1.
example 2
This example illustrates the star block copolymers of the present invention and their preparation.
(1) Under the protection of nitrogen, 700mmol of isobutylene (about 39.2g), 150mL of n-hexane and 200mL of monochloromethane are placed in a cooling bath at-60 ℃ and stirred and mixed for 30min, then 50mL of a dichloromethane solution of styrene copolymer P2 (the concentration of copolymer P1 is 5mg/mL), 20mL of a dichloromethane solution of dimethyl sulfoxide (the concentration of dimethyl sulfoxide is 0.11mmol/mL) and 8mL of a dichloromethane solution of 2, 6-di-tert-butylpyridine (the concentration of 2, 6-di-tert-butylpyridine is 0.12mmol/mL) are added and stirred and mixed for 15 min; and then 15mmol of titanium tetrachloride was added to the mixed system and the first cationic polymerization was carried out at-60 ℃ for 90min, whereby the conversion of isobutylene was 100%;
(2) preparing a styrene solution containing 2, 6-di-tert-butylpyridine to obtain a mixed solution containing 150mmol of styrene (about 15.6g), 50mL of n-hexane, 15mL of dichloromethane, and 0.8mL of a dichloromethane solution of 2, 6-di-tert-butylpyridine (the concentration of 2, 6-di-tert-butylpyridine is 0.12mmol/mL), adding the styrene solution to the first cationic polymerization reaction product obtained in step (1), and continuing to perform a second cationic polymerization reaction at-60 ℃ for 100min, thereby obtaining a conversion of styrene of 100%.
And (3) terminating the second cationic polymerization reaction product, mixing the polymer solution obtained after termination with clean water of the same volume, removing unreacted monomers and solvents at 100 ℃, washing with water for three times, naturally drying, and putting into a vacuum oven for drying until the weight is constant, thereby obtaining the copolymer A2.
The weight average molecular weight of the copolymer was identified to be 850,000g/mol, with a molecular weight distribution index of 1.96; the copolymer is of a star-shaped structure and is provided with a star-shaped central structure and an isobutylene-styrene block copolymer chain connected with the star-shaped central structure, wherein the content of the star-shaped central structure is 5 wt%, the content of the block copolymer chain is 95 wt%, and the weight average molecular weight of the block copolymer chain is 6,600 g/mol; in the block copolymer chain, the molar ratio of the structural units of isobutylene and styrene was 4.7: 1.
example 3
This example illustrates the star block copolymers of the present invention and their preparation.
Copolymer A3 was finally obtained according to the procedure described in example 1, except that a styrenic copolymer P3 was used in place of the styrenic copolymer P1 in example 1.
The weight average molecular weight of the copolymer is identified to be 365,000g/mol, and the molecular weight distribution index is 2.08; the copolymer is of a star-shaped structure and is provided with a star-shaped central structure and an isobutylene-styrene block copolymer chain connected with the star-shaped central structure, wherein the content of the star-shaped central structure is 1.1 weight percent, the content of the block copolymer chain is 98.9 weight percent, and the weight average molecular weight of the block copolymer chain is 3,600 g/mol; in the block copolymer chain, the molar ratio of the structural units of isobutylene and styrene was 3.4: 1.
example 4
This example illustrates the star block copolymers of the present invention and their preparation.
Copolymer A4 was finally obtained according to the procedure described in example 1, except that a styrenic copolymer P4 was used in place of the styrenic copolymer P1 in example 1.
The weight average molecular weight of the copolymer was identified to be 580,000g/mol, and the molecular weight distribution index was 2.68; the copolymer is of a star-shaped structure and is provided with a star-shaped central structure and an isobutylene-styrene block copolymer chain connected with the star-shaped central structure, wherein the content of the star-shaped central structure is 6.8 wt%, the content of the block copolymer chain is 93.2 wt%, and the weight average molecular weight of the block copolymer chain is 1,600 g/mol; in the block copolymer chain, the molar ratio of the structural units of isobutylene and styrene was 3.4: 1.
example 5
This example illustrates the star block copolymers of the present invention and their preparation.
The process of example 1 except that the polymerization temperature is-50 ℃; copolymer A5 was finally obtained.
The weight average molecular weight of the copolymer was identified to be 200,000g/mol, and the molecular weight distribution index was 3.20; the copolymer is of a star-shaped structure and is provided with a star-shaped central structure and an isobutylene-styrene block copolymer chain connected with the star-shaped central structure, wherein the content of the star-shaped central structure is 3 weight percent, the content of the block copolymer chain is 97 weight percent, and the weight average molecular weight of the block copolymer chain is 1,800 g/mol; in the block copolymer chain, the molar ratio of the structural units of isobutene and styrene is 3.4: 1.
comparative example 1
The process of example 1 was followed except that an equal weight portion of dicumyl chloride (formula:) was used
Prepared according to preparation example 2 of CN 106146705A) instead of the styrenic copolymer P1; copolymer DA1 was obtained.
The copolymer was a linear block copolymer having a weight average molecular weight of 160,000g/mol and a molecular weight distribution index of 1.4.
Test example 1
The tensile strength and elongation at break of the block copolymer were measured, and the results are shown in table 1; wherein the tensile strength and elongation at break are determined according to the method in GB/T528-2009.
TABLE 1
| Copolymer | Tensile strength/MPa | Elongation at break/100% |
| A1 | 28.0 | 700％ |
| A2 | 26.8 | 660％ |
| A3 | 16.5 | 410％ |
| A4 | 19.1 | 430％ |
| A5 | 15.8 | 360％ |
| DA1 | 15 | 320％ |
As can be seen from the results in Table 1, the star-shaped block copolymer (such as SBS star-shaped block copolymer) synthesized by using the styrene-based macroinitiator provided by the invention has better mechanical properties; for example, the tensile strength of the star block copolymer may be 15MPa or more, preferably 18MPa or more, more preferably 25 to 30 MPa; the elongation at break can be up to 350% or more, preferably 400% or more, more preferably 600-750%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (59)
1. A star block copolymer comprising a structure providing a star center and a block polymer chain bonded to the star center; wherein the structure providing the star center is provided by a styrene copolymer, the styrene copolymer is composed of a structural unit shown in a formula (1) and a structural unit shown in a formula (2), and the styrene copolymer contains a benzyl structure with halogen, so that a carbenium active site is easily provided, and a plurality of carbenium active sites are formed on a chain of the styrene copolymer so as to be conveniently connected with a block polymer chain; the block polymer chain comprises a block A and a block B, wherein the block polymer chain is bonded with the structure providing the star center through the block A; the block A is provided by an isomonoolefin represented by formula (3), and the block B is provided by a styrenic monomer represented by formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from H and C1-C8 alkyl; x is halogen; r is3And R4Each independently selected from C1-C5 alkyl.
2. The radial block copolymer of claim 1 wherein each R1And R2Each independently selected from H and C1-C4 alkyl; x is F, Cl, Br or I; r3And R4Each is independentIs selected from C1-C4 alkyl.
3. The radial block copolymer of claim 2 wherein each R1And R2Each independently selected from H, methyl, ethyl and n-propyl; x is Cl or Br; r3And R4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
4. The star block copolymer according to any of claims 1 to 3, wherein the content of the structure providing the star center in the star block copolymer is 1 to 10% by weight, and the content of the block polymer chain is 90 to 99% by weight.
5. The star block copolymer according to claim 4, wherein the content of the structure providing the star center in the star block copolymer is 1 to 7% by weight, and the content of the block polymer chain is 93 to 99% by weight.
6. The radial block copolymer according to any one of claims 1 to 3 and 5, wherein the molar ratio of the isomonoolefin represented by formula (3) providing structural units to the styrenic monomer represented by formula (4) providing structural units in the block polymer chain is 1 to 6: 1.
7. the radial block copolymer according to claim 6, wherein the molar ratio of the isomonoolefin represented by the formula (3) providing structural units to the styrenic monomer represented by the formula (4) providing structural units in the block polymer chain is 3 to 5: 1.
8. the radial block copolymer of claim 6 wherein the weight average molecular weight of the block polymer chain is 1,000-10,000 g/mol.
9. The radial block copolymer of claim 8 wherein the weight average molecular weight of the block polymer chain is 1,500-9,000 g/mol.
10. The radial block copolymer of claim 9 wherein the weight average molecular weight of the block polymer chain is 3,000-8,500 g/mol.
11. The radial block copolymer of claim 10 wherein the weight average molecular weight of the block polymer chain is 5,000-8,000 g/mol.
12. The radial block copolymer according to any one of claims 1 to 3,5 and 7 to 11, wherein the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) in the styrenic copolymer is 1: 0.01-0.3.
13. The radial block copolymer according to claim 12, wherein the styrene-based copolymer has a molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) of 1: 0.015-0.1.
14. The radial block copolymer according to claim 13, wherein the styrene-based copolymer has a molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) of 1: 0.03-0.08.
15. The radial block copolymer of claim 12 wherein the styrenic copolymer has a weight average molecular weight of 20,000-150,000 g/mol; the molecular weight distribution index is 1-3.
16. The radial block copolymer of claim 15 wherein the styrenic copolymer has a weight average molecular weight of 30,000-130,000 g/mol.
17. The radial block copolymer of claim 16 wherein the styrenic copolymer has a weight average molecular weight of 50,000-100,000 g/mol.
18. The radial block copolymer of claim 17 wherein the styrenic copolymer has a weight average molecular weight of 60,000-80,000 g/mol.
19. The radial block copolymer according to any of claims 1 to 3,5, 7 to 11 and 13 to 18, wherein the radial block copolymer has a weight average molecular weight of 100,000-2,000,000 g/mol; the molecular weight distribution index is 1.5-3.
20. The radial block copolymer of claim 19 wherein the radial block copolymer has a weight average molecular weight of 300,000-1,000,000 g/mol.
21. The star block copolymer of claim 20 wherein the weight average molecular weight of the star block copolymer is 350,000-980,000 g/mol.
22. The radial block copolymer of claim 21 wherein the radial block copolymer has a weight average molecular weight of 550,000-980,000 g/mol.
23. The radial block copolymer of claim 22 wherein the radial block copolymer has a weight average molecular weight of 700,000-980,000 g/mol.
24. A method for preparing a radial block copolymer, the method comprising:
(1) in the presence of Lewis acid, nucleophilic reagent and proton trapping agent, in organic solvent, styrene copolymer providing carbocation and isomonoolefin are first cationic polymerized to obtain star-shaped polyisomonoolefin polymerization system with reactive end;
(2) carrying out a second cationic polymerization reaction on the polymerization system obtained in the step (1) and a styrene monomer to obtain a star-shaped block copolymer; the star-shaped central structure of the star-shaped block copolymer is provided by the styrene copolymer, the block polymer chain bonded with the star-shaped center is provided by isomonoolefin and styrene monomer, and the styrene copolymer contains a benzyl structure with halogen, so that a carbocation active site is easily provided, and a plurality of carbocation active sites are formed on the chain of the styrene copolymer and are conveniently connected with the block polymer chain;
wherein the styrene copolymer is composed of a structural unit represented by formula (1) and a structural unit represented by formula (2);
the isomonoolefin is a compound shown in a formula (3), and the styrene monomer is a compound shown in a formula (4):
formula (1):
formula (2):
formula (3):
formula (4):
wherein each R is1And R2Each independently selected from H and C1-C8 alkyl; x is halogen; r3And R4Each independently selected from C1-C5 alkyl.
25. The method of claim 24, wherein each R is1And R2Each independently selected from H and C1-C4 alkyl; x is F, Cl, Br or I; r3And R4Each independently selected from C1-C4 alkyl.
26. The method of claim 25, wherein each R is1And R2Each independently selected from H, methyl, ethyl and n-propyl; x is Cl orBr；R3And R4Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
27. The process of any one of claims 24-26, wherein the styrenic copolymer is used in an amount of 1 to 10 wt.% and the isomonoolefin and styrenic monomer are used in an amount of 90 to 99 wt.%, based on the total weight of the styrenic copolymer, isomonoolefin, and styrenic monomer.
28. The process of claim 27, wherein the styrenic copolymer is used in an amount of 1 to 7 wt.% and the isomonoolefin and styrenic monomer are used in an amount of 93 to 99 wt.%, based on the total weight of the styrenic copolymer, isomonoolefin, and styrenic monomer.
29. A process as claimed in claim 27, wherein the isomonoolefin and styrenic monomer are used in a molar ratio of from 1 to 6: 1.
30. a process as claimed in claim 29, wherein the isomonoolefin and styrenic monomer are used in a molar ratio of from 3 to 5: 1.
31. the method according to claim 27, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the styrenic copolymer is 1: 0.01-0.3.
32. The method according to claim 31, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the styrene-based copolymer is 1: 0.015-0.1.
33. The method according to claim 32, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the styrenic copolymer is 1: 0.03-0.08.
34. The method as claimed in claim 27, wherein the styrene-based copolymer has a weight average molecular weight of 20,000-150,000 g/mol; the molecular weight distribution index is 1-3.
35. The method as in claim 34, wherein the styrenic copolymer has a weight average molecular weight of 30,000-130,000 g/mol.
36. The method as recited in claim 35, wherein the styrenic copolymer has a weight average molecular weight of 50,000-100,000 g/mol.
37. The method as claimed in claim 36, wherein the styrene-based copolymer has a weight average molecular weight of 60,000-80,000 g/mol.
38. The process of any one of claims 24-26 and 28-37, wherein the lewis acid is one or more of titanium tetrachloride, boron trifluoride, ethyl aluminum dichloride, aluminum trichloride, zinc chloride, tin dichloride, ferric trichloride, and antimony pentafluoride.
39. The process of claim 38, wherein the lewis acid is titanium tetrachloride.
40. A process as claimed in claim 38, wherein the Lewis acid is used in an amount of from 1 to 10 mol%, based on the total moles of isomonoolefin and styrenic monomer.
41. The method of any one of claims 24-26, 28-37, and 39-40, wherein the nucleophile is one or more of N, N-dimethylacetamide, dimethylsulfoxide, triethylamine, acetone, methanol, ethanol, and tert-butanol.
42. The method of claim 41, wherein the nucleophile is one or more of N, N-dimethylacetamide, dimethylsulfoxide, and triethylamine.
43. A process as claimed in claim 41, wherein the nucleophile is used in an amount of from 0.1 to 1 mol%, based on the molar total of isomonoolefin and styrenic monomers.
44. The method of claim 41, wherein the nucleophile is provided in the form of a solution thereof, the concentration of the nucleophile-containing solution is 0.01-5 mmol/L.
45. The method of any one of claims 24-26, 28-37, 39-40, and 42-44, wherein the proton scavenger is one or more of 2, 6-di-tert-butylpyridine, 2, 6-di-tert-butyl-4-methylpyridine, pyridine, and tetramethylpiperidine.
46. A process as claimed in claim 45, in which the proton scavenger is used in an amount of from 0.02 to 0.2 mol%, based on the total molar amount of isomonoolefin and styrenic monomer.
47. The method of claim 45, wherein the proton scavenger is provided in the form of a solution comprising the proton scavenger at a concentration of 0.01 to 5 mmol/L.
48. The method of any one of claims 24-26, 28-37, 39-40, 42-44, and 46-47, wherein in step (1), the organic solvent consists of a first organic solvent that is a non-halogenated alkane solvent and a second organic solvent that is a halogenated alkane solvent.
49. A process as claimed in claim 48, wherein the volume ratio of the first and second organic solvents is 100: 10-600.
50. A process according to claim 49, wherein the volume ratio of the first and second organic solvents is 100: 50-300.
51. The method as claimed in claim 48, wherein in step (1), the amount of the organic solvent is 100-1000mL relative to 1mol of the isomonoolefin.
52. The process as claimed in claim 51, wherein the amount of the organic solvent used in step (1) is 200-800mL per 1mol of the isomonoolefin.
53. The process of any of claims 24-26, 28-37, 39-40, 42-44, 46-47, and 49-52, wherein in step (2), the styrenic monomer is provided in the form of a solvent thereof, and the solution containing the styrenic monomer has a concentration of 0.1 to 5 mol/L.
54. The process as claimed in any one of claims 24 to 26, 28 to 37, 39 to 40, 42 to 44, 46 to 47 and 49 to 52, wherein in step (1), the first cationic polymerization reaction results in a conversion of isomonoolefin of 90% or more.
55. The method of claim 54, wherein the conditions of the first cationic polymerization reaction comprise: the temperature is-100 ℃ to 20 ℃; the time is 50-120 min.
56. The method of claim 55, wherein the conditions of the first cationic polymerization reaction comprise: the temperature is-100 ℃ to 0 ℃; the time is 60-100 min.
57. The method of claim 54, wherein the conditions of the second cationic polymerization reaction comprise: the temperature is-100 ℃ to 20 ℃; the time is 50-120 min.
58. The method of claim 57, wherein the conditions of the second cationic polymerization reaction comprise: the temperature is-100 ℃ to 0 ℃; the time is 60-100 min.
59. A radial block copolymer made by the process of any one of claims 24-58.
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