CN104974291A - Cationic polymerization method - Google Patents

Abstract

A cationic polymerization process is disclosed which comprises at least one dilution under cationic polymerization conditionsIn the agent, at least one monoolefin and at least one alkylstyrene are contacted with the components of an initiator system comprising at least one compound capable of providing a carbenium ion, at least one Lewis acid and at least one activator selected from the group consisting of compounds represented by formula I-1 and compounds represented by formula I-2. When the catalyst is copolymerized with monoolefine in a solution state through cationic polymerization, the method can obviously improve the copolymerization activity of the alkylstyrene, thereby improving the polymerization efficiency of a polymerization system and obtaining higher polymer yield. In addition, the method can prepare polymers with different molecular weights under different polymerization conditions by adjusting the composition of an initiator system so as to meet the requirements of different application occasions.

Description

A cationic polymerization method

technical field

The present invention relates to a cationic polymerization method.

Background technique

Brominated isobutylene-p-methylstyrene copolymer is generally obtained by brominating the copolymer of isobutylene and p-methylstyrene, and converting part of the p-methylstyrene group into bromomethylstyrene group of. Because the main chain of the molecule is a fully saturated structure, the brominated isobutylene-p-methylstyrene copolymer has better overall performance than brominated butyl rubber, especially has better heat resistance; and, due to the high activity The existence of the benzyl bromide functional group can realize vulcanization and co-vulcanization with various rubbers in a wider range, and also has a wider range of modification advantages. The product is blended with nylon to make dynamically vulcanized alloys for the production of tire innerliners, which can be light and thin, so brominated isobutylene and p-methylstyrene copolymers can be used to produce higher performance tires, and has a very broad market application prospects.

Therefore, researchers have conducted a lot of research on isobutylene and p-alkylstyrene copolymers and their halides. For example: US5162445 and US5959049 respectively disclose isobutylene and p-alkylstyrene copolymers and their preparation methods.

Contents of the invention

The inventors of the present invention found in the course of research that when isobutylene is subjected to cationic polymerization, its polymerization efficiency (that is, polymer yield) is not sensitive to the polarity of the diluent, but when isobutylene and alkylstyrene are polymerized by cationic When the copolymerization is carried out in the same way, as the polarity of the diluent decreases, the polymerization efficiency decreases, so that when the system is in a solution polymerization state (that is, with aliphatic alkanes or alicyclic alkanes as diluents), p-methylstyrene The copolymerization activity is significantly reduced, resulting in extremely poor polymerization efficiency and low polymer yield.

The inventors of the present invention have conducted research on the above problems and found that when cationic copolymerization of monoolefins and alkylstyrenes is carried out in the form of solution polymerization, if a quinoid compound is introduced into the initiator system, the polymerization efficiency can be significantly improved. This increases the yield of the polymer. The present invention has been accomplished on this basis.

The present invention provides a cationic polymerization process, which comprises mixing at least one monoolefin and at least one alkylstyrene with the components of the initiator system in at least one diluent under cationic polymerization conditions contacting, the initiator system contains at least one compound capable of providing carbocations, at least one Lewis acid and at least one activator,

The activator is selected from compounds shown in formula I-1 and compounds shown in formula I-2,

In formula I-1 and formula I-2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each -H, -X ¹ , -NO ₂ , One of and -CN, X ¹ and X ² are each a kind of halogen group;

Described Lewis acid contains the compound shown in formula II and the compound shown in formula III,

In formula II, each of R ₉ and R ₁₀ is a C ₁ -C ₈ linear or branched alkyl group, and X ³ is one of the halogen groups;

In formula III, R ₁₁ is a straight chain or branched chain alkyl group of C ₁ to C ₈ , and X ⁴ and X ⁵ are each one of halogen groups;

The monoolefin is selected from compounds shown in formula IV,

In formula IV, each of R ₁₂ and R ₁₃ is a C ₁ -C ₅ linear or branched alkyl group; or R ₁₂ is hydrogen, and R ₁₃ is a C ₃ -C ₅ branched alkyl group;

The alkyl styrene is selected from compounds shown in formula V,

In formula V, R ₁₄ is a C ₁ -C ₅ linear or branched alkyl group;

The diluent is selected from aliphatic alkanes and alicyclic alkanes.

When copolymerizing with monoolefin in a solution state through cationic polymerization, the method of the invention can obviously improve the copolymerization activity of alkylstyrene, thereby improving the polymerization efficiency of the polymerization system and obtaining higher polymer yield.

In addition, according to the method of the present invention, by adjusting the composition of the initiator system, polymers with different molecular weights can be prepared under different polymerization conditions to meet the requirements of different applications.

Detailed ways

The present invention provides a cationic polymerization process, which comprises mixing at least one monoolefin and at least one alkylstyrene with the components of the initiator system in at least one diluent under cationic polymerization conditions contact, the initiator system comprising at least one compound capable of donating carbocations, at least one Lewis acid and at least one activator.

The activator is selected from compounds shown in formula I-1 and compounds shown in formula I-2,

In formula I-1 and formula I-2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each -H, -X ¹ , -NO ₂ , and -CN, each of X1 and X2 is ^one of the halogen groups ⁽ for example: -F, -Cl, -Br or -I).

Specific examples of the activator may include, but are not limited to: tetrahydro-p-benzoquinone, tetrahydro-o-benzoquinone, monofluorotrihydro-p-benzoquinone, monofluorotrihydro-o-benzoquinone, difluorodihydro-p-benzoquinone, difluorodihydro-p-benzoquinone, Fluorodihydro-o-benzoquinone, Trifluoro-hydro-p-benzoquinone, Trifluoro-o-benzoquinone, Tetrafluoro-p-benzoquinone, Tetrafluoro-o-benzoquinone, Chlorotrihydro-p-benzoquinone, Chlorotrihydro-o-benzoquinone , Dichlorodihydro-p-benzoquinone (including 2,3-dichloro-p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone), dichlorodihydro-p-benzoquinone (including 3,4-dichloro-o-benzoquinone, 3,5-dichloro-o-benzoquinone, 3,6-dichloro-o-benzoquinone), trichloro-p-benzoquinone, trichloro-o-benzoquinone, tetrachloro-p-benzoquinone Benzoquinone, tetrachloro-o-benzoquinone, bromotrihydro-p-benzoquinone, bromotrihydro-o-benzoquinone, dibromodihydro-p-benzoquinone (including 2,3-dibromo-p-benzoquinone, 2,5-dibromo-p-benzoquinone p-benzoquinone, 2,6-dibromo-p-benzoquinone), dibromodihydro-o-benzoquinone (including 3,4-dibromo-o-benzoquinone, 3,5-dibromo-o-benzoquinone, 3,6-dibromo-o-benzoquinone o-benzoquinone), tribromo-hydro-p-benzoquinone, tribromo-hydro-o-benzoquinone, tetrabromo-p-benzoquinone, tetrabromo-o-benzoquinone, a fluorotrinitro-p-benzoquinone, a fluorotrinitro-o-benzoquinone , Difluorodinitro-p-benzoquinone (including 2,3-difluoro-5,6-dinitro-p-benzoquinone, 2,5-difluoro-3,6-dinitro-p-benzoquinone, 2,6 -difluoro-3,5-dinitro-p-benzoquinone), difluoro-dinitro-o-benzoquinone (including 3,4-difluoro-5,6-dinitro-o-benzoquinone, 3,5-difluoro -4,6-dinitro-o-benzoquinone, 3,6-difluoro-4,5-dinitro-o-benzoquinone), trifluoro-nitro-p-benzoquinone, trifluoro-nitro-o-benzoquinone, a Chlorotrinitro-p-benzoquinone, monochlorotrinitro-o-benzoquinone, dichlorodinitro-p-benzoquinone (including 2,3-dichloro-5,6-dinitro-p-benzoquinone, 2,5-di Chloro-3,6-dinitro-p-benzoquinone, 2,6-dichloro-3,5-dinitro-p-benzoquinone), dichlorodinitro-o-benzoquinone (including 3,4-dichloro-5 ,6-dinitro-o-benzoquinone, 3,5-dichloro-4,6-dinitro-o-benzoquinone, 3,6-dichloro-4,5-dinitro-o-benzoquinone), trichloro- Nitro-p-benzoquinone, trichloro-nitro-o-benzoquinone, bromotrinitro-p-benzoquinone, bromotrinitro-o-benzoquinone, dibromodinitro-p-benzoquinone (including 2,3-dibromo- 5,6-dinitro-p-benzoquinone, 2,5-dibromo-3,6-dinitro-p-benzoquinone, 2,6-dibromo-3,5-dinitro-p-benzoquinone), dibromo Dinitro-o-benzoquinone (including 3,4-dibromo-5,6-dinitro-o-benzoquinone, 3,5-dibromo-4,6-dinitro-o-benzoquinone, 3,6-dibromo-o-benzoquinone -4,5-dinitro-o-benzoquinone), tribromo-nitro-p-benzoquinone, tribromo-nitro-o-benzoquinone, tetranitro-p-benzoquinone, tetranitro-o-benzoquinone, fluorotricyano p-benzoquinone, fluorotricyano-o-benzoquinone, difluorodicyano-p-benzoquinone (including 2,3-difluoro-5,6-dicyano-p-benzoquinone, 2,5-difluoro-3, 6-dicyano-p-benzoquinone, 2,6-difluoro-3,5-dicyano-p-benzoquinone), difluorodicyano-o-benzoquinone (including 3,4-difluoro-5,6-di cyano-benzoquinone, 3,5-difluoro-4,6-dicyano-benzoquinone, 3,6-difluoro-4 ,5-dicyano-benzoquinone), trifluoro-cyano-p-benzoquinone, trifluoro-cyano-o-benzoquinone, one chlorotricyano-p-benzoquinone, one chlorotricyano-o-benzoquinone, dichlorodi Cyano-p-benzoquinone (including 2,3-dichloro-5,6-dicyano-p-benzoquinone, 2,5-dichloro-3,6-dicyano-p-benzoquinone, 2,6-dichloro- 3,5-dicyano-p-benzoquinone), dichlorodicyano-o-benzoquinone (including 3,4-dichloro-5,6-dicyano-o-benzoquinone, 3,5-dichloro-4,6 -Dicyano-o-benzoquinone, 3,6-dichloro-4,5-dicyano-o-benzoquinone), trichloro-cyano-p-benzoquinone, trichloro-cyano-o-benzoquinone, bromotricyano p-benzoquinone, bromotricyano-o-benzoquinone, dibromodicyano-p-benzoquinone (including 2,3-dibromo-5,6-dicyano-p-benzoquinone, 2,5-dibromo-3, 6-dicyano-p-benzoquinone, 2,6-dibromo-3,5-dicyano-p-benzoquinone), dibromodicyano-o-benzoquinone (including 3,4-dibromo-5,6-dibromo- cyano-benzoquinone, 3,5-dibromo-4,6-dicyano-o-benzoquinone, 3,6-dibromo-4,5-dicyano-o-benzoquinone), tribromo-cyano-p-benzoquinone Quinone, tribromo-cyano-benzoquinone, trinitro-cyano-p-benzoquinone, trinitro-cyano-benzoquinone, dinitrodicyano-p-benzoquinone (including 2,3-dinitro- 5,6-dicyano-p-benzoquinone, 2,5-dinitro-3,6-dicyano-p-benzoquinone, 2,6-dinitro-3,5-dicyano-p-benzoquinone), Dinitrodicyano-o-benzoquinone (including 3,4-dinitro-5,6-dicyano-o-benzoquinone, 3,5-dinitro-4,6-dicyano-o-benzoquinone, 3 ,6-dinitro-4,5-dicyano-benzoquinone), one-nitrotricyano-benzoquinone, one-nitrotricyano-benzoquinone, tetracyano-p-benzoquinone, tetracyano-o-benzoquinone Benzoquinone, fluorotriformyl chloride-p-benzoquinone, fluorotriformyl chloride-p-benzoquinone, difluorodiformyl chloride-p-benzoquinone (including 2,3-difluoro-5,6-diformyl chloride-p-benzoquinone , 2,5-difluoro-3,6-diformyl chloride p-benzoquinone, 2,6-difluoro-3,5-diformyl chloride p-benzoquinone), difluorodiformyl chloride o-benzoquinone ( Including 3,4-difluoro-5,6-diformyl chloride o-benzoquinone, 3,5-difluoro-4,6-diformyl chloride o-benzoquinone, 3,6-difluoro-4,5- Diformyl chloride o-benzoquinone), trifluoro-formyl chloride-p-benzoquinone, trifluoro-formyl chloride o-benzoquinone, one chlorotriformyl chloride-p-benzoquinone, one chlorotriformyl chloride o-benzoquinone, dichlorodi Formyl chloride p-benzoquinone (including 2,3-dichloro-5,6-diformyl chloride p-benzoquinone, 2,5-dichloro-3,6-diformyl chloride p-benzoquinone, 2,6- Dichloro-3,5-diformyl chloride-p-benzoquinone), dichloro-diformyl chloride-o-benzoquinone (including 3,4-dichloro-5,6-diformyl chloride-o-benzoquinone, 3,5- Dichloro-4,6-diformyl chloride-o-benzoquinone, 3,6-dichloro-4,5-diformyl chloride-o-benzoquinone), trichloro-formyl chloride-p-benzoquinone, trichloro-formyl chloride o-benzoquinone, bromotriformyl chloride-p-benzoquinone, bromotriformyl chloride-p-benzoquinone, dibromodiformyl chloride-p-benzoquinone (including 2,3-dibromo-5,6-diformyl chloride p-benzoquinone Benzoquinone, 2, 5-dibromo-3,6-diformyl chloride p-benzoquinone, 2,6-dibromo-3,5-diformyl chloride p-benzoquinone), dibromodiformyl chloride o-benzoquinone (including 3, 4-Dibromo-5,6-diformyl chloride o-benzoquinone, 3,5-dibromo-4,6-diformyl chloride o-benzoquinone, 3,6-dibromo-4,5-diformyl chloride benzoquinone), tribromoyl chloride-p-benzoquinone, tribromoyl chloride-o-benzoquinone, tetraformyl chloride-p-benzoquinone and tetraformyl chloride o-benzoquinone.

Preferably, the activator is selected from the group consisting of chloranil (including chloranil and o-benzoquinone), dichlorodicyanobenzoquinone (including dichlorodicyanoquinone and dichlorodicyanoquinone) o-benzoquinone), tetrahydrobenzoquinone (including tetrahydro-p-benzoquinone and tetrahydro-o-benzoquinone), and tetracyanobenzoquinone (including tetracyano-p-benzoquinone and tetracyano-o-benzoquinone).

The compound capable of providing carbocations may be various compounds capable of separating out carbocations by interacting with Lewis acids. Specifically, the compound capable of providing carbocations can be selected from one or more than two One or more hydrogens in substituted alkanes and aryls are replaced by Substituted arene, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each hydrogen, C ₁ -C ₈ alkyl, phenyl, C ₇ -C ₁₀ phenylalkyl, C ₇ -C ₁₀ alkyl Phenyl or C ₃ -C ₈ cycloalkyl; each of X ⁶ and X ⁷ is one of halogen groups, such as -F, -Cl, -Br or -I, preferably -Cl or -Br.

The C ₇ -C ₁₀ phenylalkyl group refers to a group formed by replacing one hydrogen atom in a C ₁ -C ₄ alkyl group with a phenyl group. Specific examples thereof include but are not limited to: benzyl, phenylethyl phenylpropyl group (wherein, propylene can be n-propylene or isopropylidene) and phenbutylene (wherein, n-butylene can be n-butylene, sec-butylene, isobutylene or tert-butylene).

The C ₇ -C ₁₀ alkylphenyl group refers to a group formed by replacing one hydrogen atom in the phenyl group with a C ₁ -C ₄ alkyl group. Specific examples thereof include but are not limited to: tolyl, ethylphenyl , propylphenyl group (wherein, propyl group can be n-propyl group or isopropyl group), butylphenyl group (wherein, butyl group can be n-butyl group, sec-butyl group, isobutyl group or tert-butyl group).

Specific examples of the C ₃ -C ₈ cycloalkyl may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

In the present invention, C ₁ -C ₈ alkyl groups include C ₁ -C ₈ straight chain alkyl groups and C ₃ -C ₈ branched chain alkyl groups. Specific examples thereof include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropane Base, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3- Dimethylbutyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl , 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3,4-dimethylpentyl, 4,4-dimethylpentyl , 2-ethylpentyl, 3-ethylpentyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methyl Dimethylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3 ,4-dimethylhexyl, 3,5-dimethylhexyl, 4,4-dimethylhexyl, 4,5-dimethylhexyl, 5,5-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-n-propylpentyl and 2-isopropylpentyl.

Specific examples of the compound capable of providing carbocations may include, but are not limited to: p-dibenzyl chloride (i.e., 1,4-bis(chloromethyl)benzene), p-dibenzyl bromide (i.e., 1,4 -bis(bromomethyl)benzene), p-dicumyl chloride (i.e., 1,4-bis(2-chloropropyl)benzene), p-dicumyl bromide (i.e., 1,4-bis(2-bromo propyl)benzene), p-dicumylmethyl ether (i.e., 1,4-bis(2-methoxypropyl)benzene), p-dibenzylmethyl ether (i.e., 1,4-bis(methoxymethyl) )benzene), and p-dicumyl acetate (i.e., 1,4-bis(2-acetoxypropyl)benzene).

Described Lewis acid contains the compound shown in formula II and the compound shown in formula III,

In formula II, R ₉ and R ₁₀ are each a C ₁ -C ₈ straight or branched chain alkyl group, each preferably a C ₁ -C ₄ straight or branched chain alkyl group; X ³ is a halogen group One, such as -F, -Cl, -Br or -I, preferably -Cl or -Br;

In formula III, R ₁₁ is a straight chain or branched chain alkyl group of C ₁ to C ₈ , each preferably a straight chain or branched chain alkyl group of C ₁ to C ₄ ; each of X ⁴ and X ⁵ is a halogen group. One, such as -F, -Cl, -Br or -I, preferably -Cl or -Br.

Specific examples of compounds shown in formula II may include, but are not limited to: dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl chloride aluminum chloride and diisobutylaluminum chloride. Preferably, the compound represented by formula II is diethylaluminum chloride.

Specific examples of compounds represented by formula III may include, but are not limited to: methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, and aluminum dichloride Aluminum isobutyl. Preferably, the compound represented by formula III is ethyl aluminum dichloride.

In the Lewis acid, the content of the compound represented by formula II and the compound represented by formula III can be properly selected according to specific polymerization conditions and expected polymer properties.

The molecular structure of the Lewis acid represented by formula II contains two alkyl groups, which can inhibit the chain transfer of the cationic active center, thereby increasing the molecular weight of the prepared polymer. However, if the content of the Lewis acid represented by formula II is too high, the polymerization reaction speed will be reduced and the polymerization time will be prolonged. Therefore, preferably, based on the total amount of Lewis acids, the content of the compound shown in formula II is 10 to 80 mol%, and the content of the compound shown in formula III is 20 to 90 mol%, so that the polymerization rate can A better balance is obtained between polymer molecular weight. More preferably, based on the total amount of Lewis acids, the content of the compound represented by formula II is 30-70 mole % (such as 50-70 mole %), and the content of the compound represented by formula III is 30-70 mole % (eg 30-50 mol%).

The relative proportions of the carbocation-donating compound, the Lewis acid and the activator can be selected according to specific polymerization conditions. Specifically, the molar ratio of the compound capable of providing carbocations to the activator may be 0.3-100:1, preferably 0.4-50:1, more preferably 0.5-20:1, and even more preferably 0.5-20:1. 5:1. The molar ratio of the Lewis acid to the activator may be 4-1000:1, preferably 5-250:1, more preferably 5-50:1.

The monoolefin and alkylstyrene can be contacted with the components of the initiator composition by various methods commonly used to carry out polymerization to form a monoolefin-alkylstyrene copolymer.

In one embodiment of the invention, the method of contacting at least one monoolefin and at least one alkylstyrene with the components of the initiator system comprises: contacting the components of the initiator system dissolving in a solvent, and aging the resulting mixture to obtain an initiator solution; mixing the initiator solution with the diluent in which the monoolefin and the alkylstyrene are dissolved.

The purpose of the aging is to make the Lewis acid in the initiator system and the compound and the activator capable of providing carbocations form a stable complex initiation active center, which can be carried out under conventional conditions. Specifically, the aging can be It is carried out in the temperature range of -100°C to 20°C, preferably in the temperature range of -100°C to 0°C, more preferably in the temperature range of -100°C to -40°C.

The aging time may be more than 10 minutes, such as 15 minutes to 10 hours. Preferably, the aging time is more than 30 minutes, such as 30 minutes to 5 hours, which can further improve the initiation activity of the prepared initiator system and further increase the polymerization activity of the polymerization system. More preferably, the aging time is more than 60 minutes, such as 60 minutes to 120 minutes, so that more excellent initiation activity can be obtained, and thus higher polymerization activity can be obtained.

The solvent may be various liquid substances capable of dissolving the carbocation-donating compound, the Lewis acid and the activator. Generally, the solvent can be selected from alkanes, halogenated alkanes and aromatic hydrocarbons; preferably selected from C ₃ -C ₁₀ alkanes, C ₁ -C ₁₀ halogenated alkanes, and C ₆ -C ₁₂ aromatic hydrocarbons; more preferably selected from C ₁ ~C ₁₀ halogenated alkanes and C ₆ ~C ₁₂ aromatic hydrocarbons. The halogen atoms in the halogenated alkanes may be chlorine, bromine or fluorine, preferably chlorine or fluorine.

Specific examples of the 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 alkanes, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethylhexane, 2,2,3-trimethylpentane , 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 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, 2,2,3-Trimethylhexane, 2,2,4- Trimethylhexane, 2,2,5-trimethylhexane, 2,3,3-trimethylhexane, 2,4,4-trimethylhexane, 2-methyl-3-ethane 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 3,3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane Hexane, trimethylcyclohexane (including various isomers of trimethylcyclohexane such as 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane , 1,2,5-trimethylcyclohexane, 1,3,5-trimethylcyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methyl Nonane, 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 Heptane, 2,2,3-trimethylheptane, 2,2,4-trimethylheptane, 2,2,5-trimethylheptane, 2,2,6-trimethylheptane alkane, 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 alkane, 1,2-diethylcyclohexane, 1,3-diethylcyclohexane, 1,4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane, Tetramethylcyclohexane (including the various isomers of tetramethylcyclohexane such as 1,2,3,4-tetramethylcyclohexane Hexane, 1,2,4,5-tetramethylcyclohexane, 1,2,3,5-tetramethylcyclohexane), monochloromethane, dichloromethane, chloroform, carbon tetrachloride , Monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexafluoride, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane , pentachloroethane, carbon hexachloride, monofluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, octafluoropropane, monochloropropane, dichloropropane, three Chloropropane, tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane, octachloropropane, monofluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, pentafluorobutane, hexafluoro Butane, heptafluorobutane, octafluorobutane, nonafluorobutane, decafluorobutane, monochlorobutane, dichlorobutane, trichlorobutane, tetrachlorobutane, pentachlorobutane, hexachlorobutane Butane, heptachlorobutane, octachlorobutane, nonachlorobutane, decachlorobutane, toluene, ethylbenzene and xylenes (including ortho-, meta- and para-xylene).

The concentration of the initiator solution can be conventionally selected and is not particularly limited. Generally, the concentration of the activator in the initiator solution may be 10-3000 ppm by weight, preferably 100-2000 ppm, more preferably 200-1500 ppm. The amount of the initiator solution can be properly selected according to the specific polymerization conditions, whichever can initiate the polymerization. Those skilled in the art can determine the amount of initiator sufficient to initiate polymerization through limited experiments under the teaching of the prior art, which will not be described in detail herein.

The monoolefin may be a monoolefin capable of cationic polymerization commonly used in the art. Generally, the monoolefin is selected from compounds shown in formula IV,

In Formula IV, each of R ₁₂ and R ₁₃ is a C ₁ -C ₅ linear or branched alkyl group; or R ₁₂ is hydrogen, and R ₁₃ is a C ₃ -C ₅ branched alkyl group.

In the present invention, C ₁ -C ₅ linear or branched chain alkyl groups include C ₁ -C ₅ straight chain alkyl groups and C ₃ -C ₅ branched chain alkyl groups, and specific examples thereof may include but are not limited to: radical, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl.

Specifically, the monoolefin may be selected from but not limited to: 2-methyl-1-propene (i.e., isobutene), 2-methyl-1-butene, 3-methyl-1-butene, 2, 3-Dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-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 and 2,4,4-Trimethyl-1-pentene.

Preferably, the monoolefin is isobutene.

The alkylstyrene is selected from the compounds shown in formula V,

In Formula V, R ₁₄ is a C ₁ -C ₅ linear or branched alkyl group.

Examples of the alkylstyrene may include, but are not limited to, p-methylstyrene, m-methylstyrene, p-ethylstyrene, and p-tert-butylstyrene.

Preferably, the alkyl styrene is selected from p-alkyl styrene shown in formula VI and m-alkyl styrene shown in formula VII,

In formula VI, R ₁₄ is a C ₁ -C ₅ linear or branched alkyl group;

In formula VII, R ₁₄ is a C ₁ -C ₅ linear or branched alkyl group.

More preferably, the alkylstyrene is p-alkylstyrene and/or m-alkylstyrene, such as p-methylstyrene and/or m-methylstyrene.

Further preferably, the content of p-alkylstyrene in the alkylstyrene is more than 80% by weight, for example, 80-100% by weight. More preferably, the content of p-alkylstyrene in the alkylstyrene is 90% by weight or more, for example, 90-100% by weight. Most preferably, the alkylstyrene is preferably p-methylstyrene.

The relative amounts of the monoolefin and the alkylstyrene can be properly selected according to the specific application of the final prepared polymer. Generally, based on the total amount of the monoolefin and alkylstyrene, the content of the monoolefin can be 80-99% by weight, preferably 90-97% by weight; the content of the alkylstyrene can be It is 1 to 20% by weight, preferably 3 to 10% by weight.

The diluent is selected from aliphatic alkanes (ie, paraffins) and cycloaliphatic alkanes (ie, naphthenes). Preferably, the diluent is selected from C ₃ -C ₁₀ aliphatic alkanes (such as C ₃ -C ₈ aliphatic alkanes) and C ₃ -C ₁₀ alicyclic alkanes. Using aliphatic and/or cycloaliphatic alkanes as diluents, the resulting polymers can be used directly in reaction steps such as bromination after an optional concentration step.

Specific examples of the diluent 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-methyl Heptane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3-ethylhexane, 2,2,3-trimethylpentane alkane, 2,3,3-trimethylpentane, 2,4,4-trimethylpentane, 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, 2,2,3-Trimethylhexane, 2,2,4 -Trimethylhexane, 2,2,5-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, 3,3-diethylpentane , 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropyl Cyclohexane, trimethylcyclohexane, n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2,3-dimethylnonane Octane, 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, 2,2,3-trimethylheptane, 2 ,2,4-Trimethylheptane, 2,2,5-Trimethylheptane, 2,2,6-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, 1,3- Diethylcyclohexane, 1,4-diethylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, tert-butylcyclohexane and tetramethylcyclohexane.

The diluent is preferably selected from n-pentane, n-hexane and n-heptane.

The amount of the diluent can be selected conventionally in the art. Generally, the diluent is used in an amount such that the total monomer concentration is 2 to 25% by weight, preferably 5 to 15% by weight.

According to the method of the present invention, the cationic polymerization conditions can be conventionally selected in the art. Generally, the conditions of the cationic polymerization include: the temperature is -120°C to 20°C, preferably -100°C to 0°C, more preferably -100°C to -40°C. According to the method of the present invention, the contact time can be conventionally selected in the art, and will not be repeated here.

According to the method of the present invention, it may also include adding a polymerization terminator to the mixture obtained after the polymerization to terminate the polymerization reaction (such as alcohol). The present invention has no particular limitation on the type and amount of the polymerization terminator, which can be a conventional choice in the field, subject to the ability to terminate the polymerization reaction, and will not be repeated here.

According to the method of the present invention, the monomers and diluents used for polymerization are preferably refined under the conditions commonly used in the art before use, which will not be repeated here.

The present invention will be described in detail below in conjunction with the examples.

In the following examples and comparative examples, the weighing method is adopted to measure the polymer yield,

Polymer yield (%)=(weight of polymer obtained/total weight of monomers added)×100%.

In the following examples and comparative examples, the molecular weight and molecular weight distribution index (M _w /M _n ) of the polymer were measured using a LC-20A liquid phase gel permeation chromatograph produced by Shimadzu Corporation of Japan, using a single-pore chromatographic column and Four-column combination. The mobile phase is tetrahydrofuran, the flow rate is 0.7mL/min; the concentration of the sample solution is 2mg/mL, and the injection volume is 200μL; the test temperature is 35°C; monodisperse polystyrene is used as the standard sample.

In the following examples and comparative examples, the proton nuclear magnetic resonance spectrum was measured using an AVANCE400 nuclear magnetic resonance instrument commercially available from Bruker, Switzerland, using CDCl ₃ as a solvent and tetramethylsilane (TMS) as an internal standard.

The solvents and monomers used in the following examples and comparative examples were refined by methods commonly used in the art before use, and the polymerization reaction and the preparation of the initiator solution were all commercially purchased from MBRAUN, Germany, equipped with a low-temperature cooling bath. in a dry box.

Examples 1 to 13 are used to illustrate the present invention.

Example 1

(1) Dissolve 0.0497g of 2,3-dichloro-5,6-dicyano-p-benzoquinone and 0.0422g of p-dibenzyl chloride in 62.1g of dichloromethane, pre-cool the resulting solution to -85°C, Then add 2.3 mL of n-hexane solution of 0.9 mol/L ethylaluminum dichloride (EADC) and 1.0 mL of toluene solution of 0.9 mol/L diethylaluminum chloride (DEAC) to this solution. Form an initiator solution, mix well and place in a cold bath at -80°C for aging. By weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 800 ppm, and the content of p-dibenzyl chloride is 680 ppm.

(2) Add 100mL of n-hexane cooled to -80°C, 11mL of isobutylene cooled to -80°C, and 0.46mL of p-methylstyrene (content: 98% by weight) at room temperature into a 250mL polymerization bottle in sequence, and mix to form monomer solution. Place the polymerization bottle in a low-temperature cooling bath at -85°C, add 8mL of the initiator solution prepared in step (1) to the monomer solution and age at -80°C for 100min, then let it stand for 40min to react, and control the cooling during the reaction. The bath temperature was in the range of -80°C to -85°C.

After the reaction was completed, 5 mL of a methanol solution containing 0.5% by weight of NaOH was added to the reaction mixture to terminate the polymerization reaction. Then, the mixed solution was placed in a hot water bath to remove the solvent, washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a polymer.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 2

Polymerization is carried out in the same manner as in Example 1, except that in the initiator solution prepared in step (1), the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone by weight is 50ppm.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Comparative example 1

Polymerization was performed using the same method as in Example 2, except that 2,3-dichloro-5,6-dicyano-p-benzoquinone was not used in step (1).

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 3

Polymerization was carried out by the same method as in Example 1, except that the initiator solution used in step (2) was prepared in step (1) and aged at -80° C. for 60 min.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 4

Polymerization was carried out in the same manner as in Example 1, except that the initiator solution used in step (2) was prepared in step (1) and aged at -80°C for 30 minutes.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 5

Polymerization was carried out by the same method as in Example 1, except that the initiator solution used in step (2) was prepared in step (1) and aged at -80° C. for 15 minutes.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 6

Polymerization was carried out in the same manner as in Example 1, except that in step (2), the temperature of the cooling bath was controlled in the range of -60°C to -70°C during the reaction.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 7

Polymerization was carried out in the same manner as in Example 1, except that in step (2), the temperature of the cooling bath was controlled to be in the range of -40°C to -50°C during the reaction.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 8

(1) Dissolve 0.0497g of 2,3-dichloro-5,6-dicyano-p-benzoquinone and 0.0422g of p-dibenzyl chloride in 62.1g of dichloromethane, pre-cool the resulting solution to -85°C, Then add 1.6mL concentration of 0.9mol/L toluene solution of 0.9mol/L diethylaluminum dichloride toluene solution and 1.6mL concentration to make initiator solution, mix After uniformity, put it in a cold bath at -80°C for aging. By weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 800 ppm, and the content of p-dibenzyl chloride is 680 ppm.

(2) Add 100mL of n-hexane cooled to -80°C, 11mL of isobutylene cooled to -80°C, and 0.46mL of p-methylstyrene (content: 98% by weight) at room temperature into a 250mL polymerization bottle in sequence, and mix to form monomer solution. Put the polymerization bottle in a low-temperature cooling bath at -85°C, add 10mL of the initiator solution prepared in step (1) to the monomer solution and age it at -80°C for 100min, then let it stand for 60min to react, and control the cooling during the reaction. The bath temperature was in the range of -80°C to -85°C.

After the reaction was completed, 5 mL of a methanol solution containing 0.5% by weight of NaOH was added to the reaction mixture to terminate the polymerization reaction. Then, the mixed solution was placed in a hot water bath to remove the solvent, washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a polymer.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 9

Polymerization was carried out in the same method as in Example 8, except that in step (1), an equal mass of tetrachloro-p-benzoquinone was used instead of 2,3-dichloro-5,6-dicyano-p-benzoquinone.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 10

Polymerization was carried out in the same manner as in Example 8, except that in step (1), 2,3-dichloro-5,6-dicyano-p-benzoquinone was replaced with an equal mass of tetrahydro-p-benzoquinone.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 11

Polymerization was carried out in the same manner as in Example 8, except that in step (1), 2,3-dichloro-5,6-dicyano-p-benzoquinone was replaced with tetracyano-p-benzoquinone of equal mass.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 12

Polymerization is carried out in the same manner as in Example 8, except that in step (1), 0.0497g of tetrachloro-p-benzoquinone and 0.0621g of p-dibenzyl bromide are dissolved in 62.1g of dichloromethane, and the resulting solution Pre-cool to -85°C, then add 1.6 mL of 0.9 mol/L dichloroethylaluminum in n-hexane and 1.6 mL of 0.9 mol/L diethylaluminum chloride in toluene to the solution Prepare an initiator solution, mix well and place in a cold bath at -80°C for aging. By weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 800ppm, and the content of p-dibenzyl bromide is 1000ppm.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Example 13

(1) Dissolve 0.0186g of 2,3-dichloro-5,6-dicyano-p-benzoquinone and 0.0422g of p-dibenzyl chloride in 62.1g of dichloromethane, pre-cool the resulting solution to -85°C, Adding 4.0mL concentration of 0.9mol/L diethylaluminum n-hexane solution and 0.44mL concentration of 0.9mol/L diethylaluminum chloride toluene solution to this solution to make initiator solution, mix After uniformity, place in a cold bath at -80°C for aging. By weight, the content of chloro-p-benzoquinone in the initiator solution is 300ppm, and the content of p-dibenzyl chloride is 680ppm.

(2) Add 200mL of n-hexane cooled to -80°C, 22mL of isobutylene cooled to -80°C and 1.26mL of p-methylstyrene cooled to -85°C into a 250mL polymerization bottle in sequence (the content is 98% by weight) , to form a monomer solution after mixing. Place the polymerization bottle in a low-temperature cooling bath at -80°C, add 15mL of the initiator solution prepared in step (1) to the monomer solution and age it at -80°C for 60 minutes, then let it stand for 100 minutes, and control the cooling during the reaction. The bath temperature was in the range of -80°C to -85°C.

After the reaction was completed, 5 mL of a methanol solution containing 0.5% by weight of NaOH was added to the reaction mixture to terminate the polymerization reaction. Then, the mixed solution was placed in a hot water bath to remove the solvent, washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a polymer.

Polymer yields, molecular weights and molecular weight distribution indices of the obtained polymers are listed in Table 1.

Claims (15)

1. a cationic polymerization process, under the method is included in cationoid polymerisation condition, in at least one thinner, by each component contacts at least one monoolefine and at least one ring-alkylated styrenes and initiator system, described initiator system contains at least one can provide the compound of carbonium ion, at least one Lewis acid and at least one activator

Described activator is selected from the compound shown in the compound shown in formula I-1 and formula I-2,

In formula I-1 and formula I-2, R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇and R ₈be-H ,-X separately ¹,-NO ₂, with the one in-CN, X ¹and X ²be the one in halogen group separately;

Described Lewis acid contains the compound shown in the compound shown in formula II and formula III,

In formula II, R ₉and R ₁₀be C separately ₁~ C ₈straight or branched alkyl, X ³for the one in halogen group;

In formula III, R ₁₁for C ₁~ C ₈straight or branched alkyl, X ⁴and X ⁵be the one in halogen group separately;

Described monoolefine is selected from the compound shown in formula IV,

In formula IV, R ₁₂and R ₁₃be C separately ₁~ C ₅straight or branched alkyl; Or R ₁₂for hydrogen, R ₁₃for C ₃~ C ₅branched-chain alkyl;

Described ring-alkylated styrenes is selected from the compound shown in formula V,

In formula V, R ₁₄for C ₁~ C ₅straight or branched alkyl;

Described thinner is selected from aliphatic alkane and alicyclic alkanes.

2. method according to claim 1, wherein, the described mol ratio of the compound of carbonium ion, described Lewis acid and described activator that can provide is 0.3 ~ 100:4 ~ 1000:1, is preferably 0.4 ~ 50:5 ~ 250:1, is more preferably 0.5 ~ 20:5 ~ 50:1.

3. method according to claim 1, wherein, the method of each component contacts at least one monoolefine and at least one ring-alkylated styrenes and described initiator system is comprised: by each components dissolved in described initiator system in solvent, and the mixture ageing that will obtain, obtain initiator solution; By described initiator solution and the mixing diluents being dissolved with described monoolefine and described ring-alkylated styrenes.

4. method according to claim 3, wherein, the time of described ageing is 15 minutes to 10 hours, is preferably more than 30 minutes, is more preferably more than 60 minutes.

5. the method according to claim 3 or 4, wherein, described ageing is carried out in the temperature range of-100 DEG C to 20 DEG C, preferably carries out in the temperature range of-100 DEG C to 0 DEG C.

6. method according to claim 3, wherein, described solvent be selected from alkane, halogenated alkane and aromatic hydrocarbons one or more.

7. according to the method in claims 1 to 3 described in any one, wherein, described activator is selected from tetrachlorobenzoquinone, DDQ, tetrahydrochysene benzoquinones and four cyano benzoquinones.

8. according to the method in claims 1 to 3 described in any one, wherein, described can provide the compound of carbonium ion be selected from by the alkane replaced and quilt the aromatic hydrocarbons replaced, R ₁₅, R ₁₆, R ₁₇and R ₁₈be hydrogen, C separately ₁~ C ₈alkyl, phenyl, C ₇~ C ₁₀phenylalkyl, C ₇~ C ₁₀alkyl phenyl or C ₃~ C ₈cycloalkyl, X ⁶and X ⁷be the one in halogen group separately, be preferably-Cl or-Br;

Preferably, the described compound of carbonium ion that can provide is to dibenzyl chlorine and/or to dibenzyl bromine.

9. method according to claim 1, wherein, the compound shown in formula II is diethyl aluminum chloride, and the compound shown in formula III is ethyl aluminum dichloride.

10. according to the method in claims 1 to 3 and 9 described in any one, wherein, with described lewis acidic total amount for benchmark, the content of the compound shown in formula II is 10 ~ 80 % by weight, and the content of the compound shown in formula III is 20 ~ 90 % by weight.

11. methods according to claim 1, wherein, with the total amount of described monoolefine and described ring-alkylated styrenes for benchmark, the content of described monoolefine is 80 ~ 99 % by weight, is preferably 90 ~ 97 % by weight; The content of described ring-alkylated styrenes is 1 ~ 20 % by weight, is preferably 3 ~ 10 % by weight.

12. according to the method in claim 1,3 and 11 described in any one, and wherein, described monoolefine is iso-butylene.

13. according to the method in claim 1,3 and 11 described in any one, and wherein, described ring-alkylated styrenes is p-methylstyrene and/or a vinyl toluene.

14. methods according to claim 1 or 3, wherein, described thinner is selected from C ₃~ C ₁₀aliphatic alkane and C ₃~ C ₁₀alicyclic alkanes.

15. methods according to claim 1, wherein, the condition of described contact comprises: temperature is-100 DEG C to 20 DEG C, is preferably-100 DEG C to 0 DEG C.