CN106146711A - A cationic polymerization method - Google Patents

Abstract

The invention discloses a cationic polymerization method, which comprises the step of contacting monoolefine shown in a formula IV and conjugated diolefin shown in a formula V with each component in an initiator system in alkane under the condition of solution polymerization, wherein the initiator system contains a compound capable of providing carbon dissociationA compound of the subgroup, Lewis acid shown in formula II and formula III and an activator, wherein the activator is selected from the compound shown in formula I-1 and the compound shown in formula I-2. And use of pure C⁺Compared with a Lewis acid initiator system, the method has high initiation efficiency and can obtain higher polymer yield at higher polymerization rate; by adjusting the composition of the initiator system, the method can obtain polymers with different molecular weights under different polymerization conditions; in addition, the method can carry out polymerization at higher temperature, and reduce energy consumption in the polymerization reaction process.

Description

A cationic polymerization method

technical field

The present invention relates to a cationic polymerization method.

Background technique

At present, the slurry polymerization method using dichloromethane as diluent is widely used in the world to produce butyl rubber. The main reason is that the slurry polymerization method has high production efficiency, and the product has high molecular weight and good processability. Compared with the slurry polymerization method, the solution polymerization method has no obvious advantages in these aspects, especially the products obtained by the solution polymerization method have low molecular weight and poor processability, so it is difficult to compete with the products obtained by the slurry polymerization method in the market . However, the development space of the solution polymerization method is relatively broad. For example, the solution polymerization method is more in line with the environmental protection requirements than the slurry polymerization method, and has a wider range of adaptation to the polymerization temperature, especially in the realization of high temperature polymerization. It has better development prospects.

However, for the production of butyl rubber in solution, the main problem is that the initiation efficiency of the initiator system is low, resulting in poor polymerization efficiency, and it is difficult to obtain high molecular weight products.

US3361725 proposes that alkyl aluminum halides are effective initiators for preparing butyl rubber in solution, and can obtain higher molecular weight products at higher temperatures, but require the molar ratio of dialkyl aluminum halides in alkyl aluminum halides It reaches more than 80%, while the molar ratio of monoalkyl aluminum dihalide is lower than 20%, thus the butyl rubber is prepared in solution (such as hexane) by the self-initiation of alkyl aluminum. However, in practice, the initiation efficiency of this initiator system is very low, and the polymerization rate is very slow, which cannot meet the needs of practical applications. For this reason, US6403747 has improved this initiator system, promptly introduces trace water or aluminoxane in above-mentioned dialkyl aluminum halide/monoalkyl aluminum dihalide mixed system, makes initiator system activity improve, thereby can The butyl rubber with a weight-average molecular weight of more than 400,000 is prepared at -60°C to -80°C. Although the initiation efficiency and polymerization rate of the initiator system disclosed in US6403747 have been improved to a certain extent, it is still unsatisfactory in the actual operation process, and the preparation of the initiator system is relatively difficult, especially the preparation technology of aluminoxane is very high. .

Therefore, for the cationic solution polymerization process of butyl rubber, it is urgent to develop a highly active initiator system suitable for solution polymerization, so as to improve the initiation efficiency and polymerization efficiency, and obtain high molecular weight products.

Contents of the invention

The object of the present invention is to provide a kind of cationic polymerization method, this method adopts solution polymerization method to prepare monoolefin-conjugated diene copolymer, can prepare monoolefin-conjugated diene copolymer with higher molecular weight with higher polymerization efficiency things.

The present invention provides a cationic polymerization method, the method comprising, under solution polymerization conditions, in at least one polymerization solvent, at least one monoolefin and at least one conjugated diene and each component in the initiator system 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 conjugated dienes are selected from compounds represented by formula V,

In formula V, each of R ₁₄ , R ₁₅ and R ₁₆ is hydrogen or a C ₁ -C ₅ linear or branched alkyl group;

The polymerization solvent is alkanes.

Adopt method of the present invention to prepare single olefin-conjugated diene copolymer, compare with adopting simple C ⁺ (that is, carbocation)/Lewis acid initiator system, on the one hand initiate efficiency obviously improves, thereby can with higher On the other hand, by adjusting the composition of the initiator system, polymers with different molecular weights can be obtained under different polymerization conditions, so as to meet the requirements of different applications. In addition, compared with the simple C ⁺ /Lewis acid initiator system, the method of the present invention can carry out polymerization at a higher temperature, thereby effectively reducing energy consumption during the polymerization reaction.

detailed description

The present invention provides a cationic polymerization method, the method comprising, under solution polymerization conditions, in at least one polymerization solvent, at least one monoolefin and at least one conjugated diene and each component in the initiator system touch.

According to the method of the invention, the initiator system comprises 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 one of -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, one-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-difluoro cyano-benzoquinone, 3,5-difluoro-4,6-dicyano-benzoquinone, 3,6-difluoro-4 , 5-dicyano-o-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-p-benzoquinone 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-di 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-o-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-o-benzoquinone), a nitrotricyano-o-benzoquinone, a nitrotricyano-o-benzoquinone, tetracyano-o-benzoquinone, tetracyano-o-benzoquinone Benzoquinone, fluorotriformyl chloride p-benzoquinone, fluorotriformyl chloride o-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 o-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-dibromoyl-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.

The activator is preferably selected from tetrahydrobenzoquinone (comprising tetrahydro-p-benzoquinone and tetrahydro-o-benzoquinone), tetrachloranil (comprising tetrahydro-p-benzoquinone and tetrahydro-o-benzoquinone), tetracyanobenzoquinone (including tetracyano-p-benzoquinone and tetracyano-o-benzoquinone) and dichlorodicyanobenzoquinone (including dichlorodicyano-p-benzoquinone and dichlorodicyano-o-benzoquinone).

The compound capable of providing carbocations may be various compounds capable of separating out carbocations by interacting with Lewis acids. Preferably, the compound capable of providing carbocations can be selected from the group consisting of one or more than two hydrogen atoms each One or more hydrogen atoms in substituted alkanes and aryls are each replaced by Substituted arene, R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ 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 Heptyl, 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: 2-chloro-2,4,4-trimethylpentane (TMPCl), benzyl chloride, benzyl bromide, p-dibenzyl chloride (i.e., 1,4-bis(chloromethyl)benzene), p-dibenzyl bromide (i.e., 1,4-bis(bromomethyl)benzene), cumyl chloride (i.e., 2-chloroisopropylbenzene ), cumyl bromide (i.e., 2-bromoisopropylbenzene), p-dicumyl chloride (i.e., 1,4-di(2-chloroisopropyl)benzene), p-dicumyl bromide (i.e., 1 , 4-bis(2-bromoisopropyl)benzene), 1,4-bis(1-chloroethyl)benzene, 1,4-bis(1-bromoethyl)benzene, tricumyl chloride (ie, 1,3,5-tris(2-chloroisopropyl)benzene) and tricumyl bromide (ie, 1,3,5-tris(2-bromoisopropyl)benzene).

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 chain alkyl group, each preferably a C ₁ -C ₄ linear or branched chain alkyl group, more preferably ethyl; X ³ Is one of the halogen groups, 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 , more preferably an ethyl group; each of X ⁴ and X ⁵ is one of the halogen groups, 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 rate will be reduced and the polymerization time will be prolonged. Therefore, preferably, based on the total amount of Lewis acid, 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 reaction 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 mol%, and the content of the compound represented by formula III is 30-70 mol%. Under the premise of obtaining a higher rate of polymerization, from the perspective of further improving the molecular weight of the prepared monoolefin-conjugated diene copolymer, based on the total amount of Lewis acid, the content of the compound shown in formula II is 50-70 mol%, and the content of the compound represented by formula III is 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 0.1 to 100:1, preferably 0.15 to 50:1, more preferably 0.2 to 20:1, and even more preferably 0.2 to 50:1. 5:1, more preferably 0.2-2.5:1, such as 0.2-1:1. The molar ratio of the Lewis acid to the activator may be 4-1000:1, preferably 5-250:1, more preferably 5-50:1, further preferably 8-25:1, such as 10-20 : 1.

The monoolefin and conjugated diene can be contacted with the components of the initiator system for polymerization to form a monoolefin-conjugated diene copolymer by various methods commonly used.

In one embodiment of the present invention, each component in the initiator system can be dissolved in a solvent, and the obtained mixture is aged to obtain an initiator solution; The monoolefin and the conjugated diene are mixed in a solvent.

The purpose of the aging is to make the Lewis acid in the initiator system form a stable active center for complexation initiation with the compound capable of providing carbocations and the activator, which can be carried out under conventional conditions. Generally, the aging can be carried out at a temperature ranging from -100°C to 20°C, preferably from -100°C to 0°C, more preferably from -100°C to -50°C, further preferably from -90°C to -70°C. The aging time may be 15 minutes to 10 hours. From the perspective of further improving the initiation efficiency of the initiator system, the aging time is preferably more than 30 minutes, for example, 30 minutes to 5 hours. More preferably, the aging time is more than 60 minutes, such as 60 minutes to 120 minutes.

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 one or more 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 One or more of ₁₂ aromatic hydrocarbons.

As a solvent, the alkanes include aliphatic alkanes and alicyclic alkanes, such as C ₃ -C ₁₀ alkanes include C ₃ -C ₁₀ aliphatic alkanes and C ₃ -C ₁₀ alicyclic alkanes.

As a solvent, the halogenated alkanes include halogenated aliphatic alkanes and halogenated cycloaliphatic alkanes, such as C ₁ to C ₁₀ halogenated alkanes include C ₁ to C ₁₀ halogenated aliphatic alkanes and C ₃ to C ₁₀ halogenated alkanes Cycloaliphatic alkanes. The halogen atoms in the halogenated alkanes may be chlorine, bromine or fluorine, preferably chlorine or fluorine. The halogenated alkane is preferably a C ₁ -C ₄ halogenated aliphatic alkane.

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 alkane, 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 various isomers of tetramethylcyclohexane, such as 1,2,3,4-tetramethylcyclohexane Hexane, 1,2,4,5-tetramethylcyclohexane, 1,2,3,5-tetramethylcyclohexane), monofluoromethane, difluoromethane, trifluoromethane, carbon tetrafluoride , monochloromethane, dichloromethane, chloroform, carbon tetrachloride, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, carbon hexafluoride, monochloro Ethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, carbon hexachloride, monofluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane Propane, Heptafluoropropane, Octafluoropropane, Monochloropropane, Dichloropropane, 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, decachlorobutane, toluene, ethylbenzene and xylene (including ortho xylene, m-xylene, and p-xylene).

The concentration of the initiator solution can be conventionally selected and is not particularly limited. 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.

According to the polymerization method of the present invention, the monoolefin may be a monoolefin commonly used in the art capable of cationic polymerization. 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.

According to the method of the present invention, the conjugated diene refers to a compound containing conjugated double bonds in its molecular structure. Preferably, the conjugated dienes are selected from compounds represented by formula V,

In Formula V, R ₁₄ , R ₁₅ and R ₁₆ are the same or different, and each is hydrogen or a C ₁ -C ₅ linear or branched alkyl group.

Specific examples of the conjugated diene may include, but are not limited to, butadiene and/or isoprene. More preferably, the conjugated diene is isoprene.

According to the method of the present invention, the relative amounts of the monoolefin and the conjugated diene can be properly selected according to the specific application of the final prepared polymer. Generally, based on the total amount of the monoolefin and the conjugated diene, the content of the monoolefin may be 80 to 99.5% by weight, preferably 90 to 98% by weight; the content of the conjugated diene may be It is 0.5 to 20% by weight, preferably 2 to 10% by weight.

According to the polymerization method of the present invention, the polymerization solvent is at least one alkane. The alkanes may be aliphatic alkanes (ie, paraffins) and/or cycloaliphatic alkanes (ie, naphthenes). The aliphatic alkane is preferably a C ₃ -C ₁₀ aliphatic alkane, more preferably a C ₃ -C ₈ aliphatic alkane, further preferably a C ₅ -C ₈ aliphatic alkane; the alicyclic alkane is preferably It is a C ₃ -C ₁₀ alicyclic alkane, more preferably a C ₅ -C ₁₀ alicyclic alkane.

As a polymerization solvent, the alkane can not only dissolve monoolefin and conjugated diene, but also dissolve the resulting monoolefin-conjugated diene copolymer, so that the polymerization reaction can be carried out under solution polymerization conditions. Specific examples of the polymerization 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-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, t-butylcyclohexane and tetramethylcyclohexane.

The polymerization solvent is preferably one or more of n-pentane, n-hexane and n-heptane.

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

According to the polymerization method of the present invention, the conditions for contacting at least one monoolefin and at least one conjugated diene with the components in the initiator system in the polymerization solvent can be selected conventionally in the art. Generally, the contacting may be performed at a temperature ranging from -120°C to 20°C, preferably from -100°C to 0°C, more preferably from -90°C to -40°C. According to the polymerization method of the present invention, the contact time can be conventionally selected in the field, and generally can be 10-180 minutes.

According to the polymerization method of the present invention, it may further 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 method according to the present invention can prepare monoolefin-conjugated diene copolymers with higher polymerization efficiency, especially monoolefin-conjugated diene copolymers with higher molecular weight can be prepared.

Specifically, in a preferred embodiment of the present invention, the compound capable of providing carbocations is 2-chloro-2,4,4-trimethylpentane, based on the total amount of Lewis acids, The content of the compound shown in formula II (preferably diethylaluminum chloride) is 30-70 mol%, the content of the compound shown in formula III (preferably dichloroethylaluminum) is 30-70 mol%, and the polymerization The reaction was carried out at a temperature ranging from -120°C to -60°C. This enables the production of a monoolefin-conjugated diene copolymer having a weight average molecular weight of 2×10 ⁵ or more. From the viewpoint of further increasing the molecular weight of the prepared monoolefin-conjugated diene copolymer, the polymerization reaction is preferably carried out at a temperature ranging from -120°C to -80°C, more preferably -90°C to -80°C. From the point of view of further improving the polymerization efficiency, the content of the compound shown in formula II (preferably diethylaluminum chloride) is 30 to 50 mol%, and the content of the compound shown in formula III (preferably dichloroethylaluminum) The content is 50-70 mol%. According to this preferred embodiment, the type of activator is not limited, and may be one or more than two of the above-mentioned activators, preferably tetrachlorobenzoquinone and/or dichlorodicyanobenzoquinone. More preferably, the activator is dichlorodicyanobenzoquinone, and the monoolefin-conjugated diene copolymer prepared in this way has a higher molecular weight, which can reach more than 3.5×10 ⁵ , and can even reach 4×10 ⁵ above. In this preferred embodiment, the ratio of the components in the initiator solution is not particularly limited, and may be the ratio described above. Preferably, the molar ratio of the compound capable of providing carbocations, the Lewis acid to the activator is 0.2-1:10-20:1. More preferably, the molar ratio of the compound capable of providing carbocations, the Lewis acid to the activator is 0.3-0.6:10-15:1. According to this preferred embodiment, the remaining conditions are not particularly limited, and may be the conditions described above.

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 of the polymer were measured by a LC-20A liquid phase gel permeation chromatograph produced by Shimadzu Corporation, using a single-aperture 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 AVANCE400 nuclear magnetic resonance instrument commercially available from the Swiss Bruker company is adopted, with _CDCl3 as solvent, TMS as internal standard, and the degree of unsaturation of the prepared monoolefin-conjugated diene copolymer (i.e. , the content of structural units formed from isoprene in the prepared monoolefin-conjugated diene copolymer).

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 carried out in a nitrogen operating box equipped with a low-temperature cooling bath.

Preparations 1-3 are used to prepare compounds capable of providing carbocations.

Preparation Example 1: Synthesis of 2-chloro-2,4,4-trimethylpentane (TMPCl)

A 250 mL round-bottomed three-neck flask was placed in an ice-water bath, and then 30 mL of 2,4,4-trimethyl-1-pentene and 30 mL of dichloromethane were added. Under the condition of continuously feeding dry hydrogen chloride gas, the reaction was carried out for 5h. The mixture obtained by the reaction was neutralized with sodium bicarbonate, then anhydrous magnesium sulfate was added to the solution, and then filtered, the liquid mixture was collected, and vacuum distillation was carried out to collect the fraction at 44°C (2.1332kPa) (yield: 70 % by weight, its purity was determined to be 93% by gas chromatography analysis). After characterization, it was confirmed that the fraction was 2-chloro-2,4,4-trimethylpentane. Among them, ¹ H-NMR (δ, ppm): 1.06 (-C(CH ₃ ) ₃ ), 1.67 (-C(CH ₃ ) ₂ Cl), 1.88 (-CH ₂ -).

Preparation Example 2: Synthesis of Dicumyl Chloride

Put a 500mL three-necked round-bottomed cauldron equipped with bottomed inlet and outlet pipes and a magnetic stirring device in an ice-water bath, and then add 8g of p-dicumyl alcohol, 10g of CaCl ₂ and 100g of dichloromethane respectively. Continuously feed dry hydrogen chloride gas into the three-necked flask, and stir and react for 10 hours. After the reaction was completed, it was filtered to obtain a clear solution. Hydrogen chloride and methylene chloride were removed in vacuo to obtain 9.1 g of colorless needle crystals (yield: 96% by weight). Dissolve the obtained needle-shaped crystals in 50 mL of n-hexane, filter to remove insoluble impurities, cool the remaining liquid phase to -20°C to -30°C, crystallize with stirring, separate the precipitated crystals from the mother liquor, and collect the crystals. The crystal was determined to be p-dicumyl chloride through characterization. Among them, ¹ H-NMR (δ, ppm): 2.00 ( ), 7.56 (phenyl).

Preparation Example 3: Synthesis of p-dicumyl bromide

p-Dicumyl bromide was prepared in a method similar to Preparation Example 2, except that hydrogen chloride gas was replaced by hydrogen bromide gas. Among them, ¹ H-NMR (δ, ppm): 2.11 ( ), 7.06 (phenyl).

Examples 1-20 are used to illustrate the present invention.

Example 1

(1) 0.0662g tetrachloro-p-benzoquinone is dissolved in 80g and contains 2-chloro-2,4,4-trimethylpentane (content is 0.018g) in the dichloromethane solution, the solution obtained is pre-cooled to -80°C, and then sequentially added 2.6 mL of n-hexane solution of ethylaluminum dichloride (EADC) with a concentration of 0.9 mol/L and 1 mL of diethylaluminum chloride (DEAC) with a concentration of 1.0 mol/L ) n-heptane solution, after mixing uniformly, aging the obtained mixed solution at -80° C. for 80 min to obtain an initiator solution. Wherein, by weight, the content of chloro-p-benzoquinone in the initiator solution is 800ppm.

(2) Place a 250mL three-necked flask in a low-temperature cooling bath whose temperature is controlled from -80°C to -85°C, and add 85mL of n-hexane cooled to -80°C, 15mL of isobutylene cooled to -80°C and 0.5 mL of isoprene pre-cooled to -20°C was mixed uniformly to obtain a monomer solution. Add 10mL of the initiator solution prepared in step (1) to the monomer solution, mix well and let it stand for 30 minutes to react, add the initiator solution dropwise and control the temperature of the cooling bath in the range of -80°C to -85°C during the reaction Inside. 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, the obtained solid was washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a monoolefin-conjugated diene copolymer.

The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 2

Polymerization is carried out in the same manner as in Example 1, except that in step (2), the temperature of the cold bath is controlled to be in the range of -40°C to -50°C during the dropwise addition of the initiator solution and the polymerization reaction Inside. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 1.

Example 3

Adopt the method identical with embodiment 1 to carry out polymerization, difference is, in step (1), the concentration of the n-hexane solution of EADC is 0.9mol/L, consumption is 1.9mL, the concentration of the n-heptane solution of DEAC is 1.0mol /L, the dosage is 1.7mL. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 1.

Example 4

Adopt the same method as Example 3 to carry out polymerization, the difference is that in step (2), the temperature of the cold bath is controlled to be in the range of -60 ° C to -70 ° C during the dropwise addition of the initiator solution and the polymerization reaction Inside. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 1.

Example 5

Adopt the method identical with embodiment 1 to carry out polymerization, difference is, in step (1), the concentration of the n-hexane solution of EADC is 0.9mol/L, consumption is 1.1mL, the concentration of the n-heptane solution of DEAC is 1.0mol /L, the dosage is 2.3mL. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 1.

Example 6

(1) Dissolve 0.0602g of 2,3-dichloro-5,6-dicyano-p-benzoquinone in 80g of 2-chloro-2,4,4-trimethylpentane (0.018g content) In the dichloromethane solution, pre-cool the resulting solution to -85°C, and then sequentially add 2.8 mL of a 0.9 mol/L n-hexane solution of dichloroethylaluminum and 1.1 mL of a 1.0 mol/L n-hexane solution to the solution. L of n-heptane solution of diethylaluminum chloride was uniformly mixed, and the obtained mixed solution was placed in a cold bath at -85° C. for aging for 100 minutes, thereby obtaining an initiator solution. Wherein, by weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 730ppm.

(2) Place a 250mL three-necked flask in a low-temperature cooling bath whose temperature is controlled from -80°C to -85°C, and add 85mL of n-hexane cooled to -80°C, 15mL of isobutylene cooled to -80°C and 0.5 mL of isoprene pre-cooled to -20°C was mixed uniformly to obtain a monomer solution. Add 10mL of the initiator solution prepared in step (1) to the monomer solution, mix well and let it stand for 30 minutes to react, add the initiator solution dropwise and control the temperature of the cooling bath in the range of -80°C to -85°C during the reaction Inside. 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, the obtained solid was washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a monoolefin-conjugated diene copolymer. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Comparative example 1

Adopt the method identical with embodiment 6 to carry out polymerization, difference is, in step (1), do not use 2,3-dichloro-5,6-dicyano-p-benzoquinone, promptly prepared initiator solution does not contain 2 , 3-dichloro-5,6-dicyano-p-benzoquinone. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Comparative example 2

Adopt the same method as Example 6 to carry out polymerization, the difference is that in step (1), under the condition that the total molar weight of Lewis acid is constant, diethylaluminum chloride is not used, that is, diethylaluminum chloride is used in an equimolar amount ethylaluminum chloride instead. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 7

Adopt the same method as Example 6 to carry out polymerization, the difference is that in step (2), the temperature of the cooling bath is controlled to be in the range of -60°C to -70°C during the dropwise addition of the initiator solution and the polymerization reaction Inside. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 8

Adopt the method identical with embodiment 6 to carry out polymerization, difference is, in step (1), the concentration of the n-hexane solution of EADC is 0.9mol/L, consumption is 2mL, the concentration of the n-heptane solution of DEAC is 1.0mol/L L, the dosage is 1.8mL. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 9

Polymerization is carried out in the same manner as in Example 8, except that in step (2), the temperature of the cold bath is controlled to be in the range of -60°C to -70°C during the dropwise addition of the initiator solution and the polymerization reaction Inside. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 10

Polymerization is carried out in the same manner as in Example 8, except that in step (2), the temperature of the cold bath is controlled to be in the range of -40°C to -50°C during the dropwise addition of the initiator solution and the polymerization reaction Inside. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 11

Adopt the same method as Example 6 to carry out polymerization, the difference is that in step (1), the concentration of the n-hexane solution of EADC is 0.9mol/L, and the consumption is 1.2mL, and the concentration of the n-heptane solution of DEAC is 1.0mol /L, the dosage is 2.5mL. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 12

Polymerization was carried out in the same manner as in Example 6, except that in step (1), the aging time was 60 min. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 13

Polymerization was carried out in the same manner as in Example 6, except that in step (1), the aging time was 30 min. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Example 14

Polymerization was carried out in the same manner as in Example 6, except that in step (1), the aging time was 15 min. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and the degree of unsaturation of the polymer were determined. The results are listed in Table 1.

Table 1

Example 15

(1) 0.065g 2,3-dichloro-5,6-dicyano-p-benzoquinone is dissolved in 80g and contains p-dicumyl chloride (content is 0.014g) in dichloromethane solution, the obtained solution Pre-cool to -85°C, and then sequentially add 2.8 mL of 0.9 mol/L ethylaluminum dichloride (EADC) n-hexane solution and 1.1 mL of 1.0 mol/L diethyl chloride After the n-heptane solution of aluminum (DEAC) is mixed evenly, the obtained mixed solution is placed in a cold bath at -85° C. for aging for 100 minutes, thereby obtaining an initiator solution. Wherein, by weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 780ppm.

(2) Place a 250mL three-necked flask in a low-temperature cooling bath whose temperature is controlled from -80°C to -85°C, and add 85mL of n-hexane cooled to -80°C, 15mL of isobutylene cooled to -80°C and 0.5 mL of isoprene pre-cooled to -20°C was mixed uniformly to obtain a monomer solution. Add 10mL of the initiator solution prepared in step (1) to the monomer solution, mix well and let it stand for 30 minutes to react, add the initiator solution dropwise and control the temperature of the cooling bath in the range of -80°C to -85°C during the reaction Inside. 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, the obtained solid was washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a monoolefin-conjugated diene copolymer.

The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Comparative example 3

Polymerization is carried out in the same manner as in Example 15, except that 2,3-dichloro-5,6-dicyano-p-benzoquinone is not used in step (1), that is, the prepared initiator solution does not contain 2, 3-dichloro-5,6-dicyano-p-benzoquinone. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Example 16

(1) 0.065g 2,3-dichloro-5,6-dicyano-p-benzoquinone is dissolved in 80g and contains benzyl chloride (content is 0.016g) in methylene chloride solution, the solution obtained is pre-cooled to -85°C, and then sequentially added 2.8 mL of n-hexane solution of 0.9 mol/L ethylaluminum dichloride (EADC) and 1.1 mL of 1.0 mol/L diethylaluminum chloride ( DEAC) n-heptane solution, after mixing evenly, place the obtained mixed solution in a cold bath at -85° C. to age for 100 min, thereby obtaining an initiator solution. Wherein, by weight, the content of 2,3-dichloro-5,6-dicyano-p-benzoquinone in the initiator solution is 780ppm.

(2) Place a 250mL three-necked flask in a low-temperature cooling bath whose temperature is controlled from -80°C to -85°C, and add 85mL of n-hexane cooled to -80°C, 15mL of isobutylene cooled to -80°C and 0.5 mL of isoprene pre-cooled to -20°C was mixed uniformly to obtain a monomer solution. Add 10mL of the initiator solution prepared in step (1) to the monomer solution, mix evenly and let it stand for 30 minutes to react. During the reaction, control the cooling bath temperature to be within 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, the obtained solid was washed with water, and then dried in a vacuum oven at 60° C. to constant weight to obtain a monoolefin-conjugated diene copolymer.

The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight and molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Comparative example 4

Polymerization is carried out in the same method as in Example 16, except that in step (1), 2,3-dichloro-5,6-dicyano-p-benzoquinone is not used, that is, the prepared initiator solution does not contain 2 , 3-dichloro-5,6-dicyano-p-benzoquinone. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Example 17

Polymerization was carried out in the same manner as in Example 16, except that in step (1), 2,3-dichloro-5,6-dicyano-p-benzoquinone was replaced by tetrahydro-p-benzoquinone in an equimolar amount.

The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Example 18

Polymerize using the same method as in Example 16, except that in step (1), 2,3-dichloro-5,6-dicyano-p-benzoquinone is replaced by tetracyano-p-benzoquinone in an equimolar amount .

The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Example 19

Polymerization was carried out in the same manner as in Example 16, except that in step (1), the aging time was 30 min. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

Example 20

Polymerization was carried out in the same manner as in Example 16, except that in step (1), the aging time was 15 min. The weight of the obtained polymer was measured, the polymer yield was calculated, and the molecular weight, molecular weight distribution index and degree of unsaturation of the polymer were determined, and the results are listed in Table 2.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (15)

1. A cationic polymerization process comprising contacting under solution polymerization conditions in at least one polymerization solvent, at least one monoolefin and at least one conjugated diolefin 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,

the activator is selected from a compound shown as a formula I-1 and a compound shown as a formula I-2,

in the formulae I-1 and I-2, R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Each is-H, -X¹、-NO₂、And one of-CN, X¹And X²Each is one of halogen groups;

the Lewis acid contains a compound shown as a formula II and a compound shown as a formula III,

in the formula II, R₉And R₁₀Each is C₁～C₈Straight or branched alkyl of, X³Is one of halogen groups;

in the formula III, R₁₁Is C₁～C₈Straight or branched alkyl of, X⁴And X⁵Each is one of halogen groups;

the monoolefin is selected from the group consisting of compounds represented by formula IV,

in the formula IV, R₁₂And R₁₃Each is C₁～C₅Linear or branched alkyl of (a); or R₁₂Is hydrogen, R₁₃Is C₃～C₅A branched alkyl group of (a);

the conjugated diene is selected from compounds shown in formula V,

in the formula V, R₁₄、R₁₅And R₁₆Each is hydrogen or C₁～C₅Linear or branched alkyl of (a);

the polymerization solvent is an alkane.

2. The method according to claim 1, wherein the molar ratio of the compound capable of providing a carbenium ion to the activator is 0.1 to 100: 1, preferably 0.15 to 50: 1, more preferably 0.2 to 20: 1, more preferably 0.2 to 5: 1, more preferably 0.2 to 2.5: 1.

3. the process according to claim 1, wherein the molar ratio of the lewis acid to the activator is from 4 to 1000: 1, preferably 5 to 250: 1, more preferably 5 to 50: 1, more preferably 8 to 25: 1.

4. the process of claim 1, wherein the contacting of at least one monoolefin and at least one conjugated diolefin with the components of the initiator system comprises: dissolving each component in the initiator system in a solvent, and aging the obtained mixture to obtain an initiator solution; mixing said initiator solution with said monoolefin and said conjugated diolefin dissolved in a polymerization solvent.

5. Process according to claim 4, wherein the aging time is from 15 minutes to 10 hours, preferably 30 minutes or more, more preferably 60 minutes or more, further preferably from 60 minutes to 120 minutes.

6. Process according to claim 4 or 5, wherein the aging is carried out at a temperature in the range of-100 ℃ to 20 ℃, preferably in the range of-100 ℃ to 0 ℃, more preferably in the range of-100 ℃ to-50 ℃, even more preferably in the range of-90 ℃ to-70 ℃.

7. The method according to claim 4 or 5, wherein the solvent is one or more selected from alkanes, halogenated alkanes and aromatic hydrocarbons.

8. A process according to any one of claims 1 to 5 wherein the activator is selected from chloranil, dichlorodicyanoquinone, tetrahydrobenzoquinone and tetracyanobenzoquinone.

9. A process according to any one of claims 1 to 5, wherein the compound capable of providing a carbenium ion is selected from the group consisting ofSubstituted alkanes and substituted amidesSubstituted aromatic hydrocarbons, R₁₇、R₁₈、R₁₉And R₂₀Each is hydrogen, C₁～C₈Alkyl, phenyl, C₇～C₁₀Phenylalkyl of C₇～C₁₀Alkyl phenyl or C₃～C₈Cycloalkyl of, X⁶And X⁷Each is one of the halogen groups, preferably-Cl or-Br;

preferably, the compound capable of providing a carbenium ion is selected from the group consisting of 2-chloro-2, 4, 4-trimethylpentane, 1, 4-bis (2-chloroisopropyl) benzene, 1, 4-bis (2-bromoisopropyl) benzene, benzyl chloride and benzyl bromide.

10. The method according to any one of claims 1 to 5, wherein the compound represented by formula II is diethyl aluminum chloride, and the compound represented by formula III is ethyl aluminum dichloride.

11. The method according to any one of claims 1 to 5, wherein the compound represented by formula II is contained in an amount of 10 to 80% by weight, preferably 30 to 70% by mole, and more preferably 50 to 70% by mole, and the compound represented by formula III is contained in an amount of 20 to 90% by weight, preferably 30 to 70% by mole, and more preferably 30 to 50% by mole, based on the total amount of the Lewis acid.

12. A process according to claim 1, wherein the monoolefin is present in an amount of from 80 to 99.5 wt%, preferably from 90 to 98 wt%, based on the total amount of monoolefin and conjugated diolefin; the content of the conjugated diene is 0.5 to 20 wt%, preferably 2 to 10 wt%.

13. The process of any one of claims 1 to 5 and 12, wherein the monoolefin is isobutylene; and/or

The conjugated diene is isoprene.

14. The process of any one of claims 1 to 5 and 12, wherein the polymerization solvent is selected from C₃～C₁₀Of (2) an aliphatic alkane.

15. The process of any one of claims 1 to 5 and 12, wherein the contacting is carried out at a temperature in the range of-100 ℃ to 20 ℃, preferably-100 ℃ to 0 ℃, more preferably-90 ℃ to-40 ℃.