CN111171197A - Method for preparing high-activity polyisobutylene by using bifunctional initiator and application - Google Patents

Method for preparing high-activity polyisobutylene by using bifunctional initiator and application Download PDF

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CN111171197A
CN111171197A CN202010087057.5A CN202010087057A CN111171197A CN 111171197 A CN111171197 A CN 111171197A CN 202010087057 A CN202010087057 A CN 202010087057A CN 111171197 A CN111171197 A CN 111171197A
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ether
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polyisobutylene
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伍一波
吴康达
李树新
郭文莉
商育伟
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Beijing Institute of Petrochemical Technology
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Abstract

The invention belongs to the technical field of synthesis of high-molecular homopolymers, and particularly relates to a method for preparing high-activity polyisobutylene with exo-olefin terminal groups at two ends by cationic polymerization of a bifunctional initiator, the method takes isobutene as a raw material, under the temperature condition of minus 30 ℃ to 10 ℃, preparing high-activity polyisobutylene through cationic polymerization in different bifunctional initiator initiating systems and different charging sequences, wherein two ends of the prepared high-activity polyisobutylene are respectively provided with exo-olefin terminal group, the content range of external olefin structures at the two ends is 70-99 mol%, the conversion rate of the isobutylene is 60-100%, the number average molecular weight of the high-activity polyisobutylene is controllable, the number average molecular weight range is 500-5000g/mol, the molecular weight distribution is narrow, and the molecular weight distribution range is 1.5-3.0. The bifunctional initiator can be prepared at low cost, and the preparation method has the advantages of simple preparation process, good repeatability and easy realization of industrial production.

Description

Method for preparing high-activity polyisobutylene by using bifunctional initiator and application
Technical Field
The invention belongs to the technical field of synthesis of high-molecular homopolymers, and particularly relates to a method for preparing high-activity polyisobutylene with exo-olefin terminal groups at two ends by cationic polymerization of a bifunctional initiator.
Background
Polyisobutylene (PIB) is a representative product of cationic polymerization, low molecular weight Polyisobutylene (PIB) (Mn 500-5000 g/mol) is the most important industrial product in isobutylene polymers, and is mainly used for the production of motor oil and fuel additives for vehicles, accounting for 75-80% of the total polyisobutylene market share.
the high-activity polyisobutene has high reactivity, good thermal stability, chemical resistance, weather resistance and cracking carbon residue-free performance compared with the conventional polyisobutene, and is widely used in the fields of lubricating oil additives, two-stroke engine oil, electric insulating materials, adhesives, putty glue sealing pastes and other high polymer blending modification, the high-activity polyisobutene has a unique terminal alkenyl structure, can be used as a macromolecular monomer, can be further reacted to obtain a plurality of useful derivatives, can be used as a macromolecular monomer to prepare a high-activity polyisobutene which has a better anti-ash and anti-oxidation property, can be used as a high-activity polyisobutene dispersant for a long-term combustion reaction to prepare a high-activity polyisobutene with a low ash content of an ashless reactive polyamine, has a better anti-ash and anti-oxidation property when the content of terminal α -double bonds at the tail end of a polyisobutene chain is higher than that of the polyisobutylene chain, is higher than that of the polyisobutylene chain end of the reactive chain, is higher than that of the polyisobutylene chain, is the most important standard in the quality of reactive polyisobutylene product quality of the reactive polyisobutylene product of the reactive polyisobutylene, the reactive polyisobutylene product, the reactive polyisobutylene under the reactive polyisobutylene, the high-CH 3, the high-CH-H high-H, the high-H high-free from the high-H-free from the high-chlorine-free from the counter ion, the high-reactive polyamine, the low-reactive polyamine, the high-reactive.
Currently, the commercial highly reactive polyisobutylene is prepared by BASF corporation, and BF is adopted in CN00130281.7 and other patents3And (4) synthesizing HRPIB by using the complex catalyst. In the published art, isobutene is used in BF3The polymerization reaction is carried out under the initiation system of (1), and the high-activity polyisobutene with various molecular weights is generated by controlling the reaction time and the reaction temperature. BF used3The complex initiating system is usually initiated by BF3the HRPIB prepared by matching with a secondary alcohol with 3-20 carbon atoms or a tertiary ether with 4-20 carbon atoms (at least one tertiary carbon atom is connected with an oxygen atom in the ether) has the α -double bond content of more than or equal to 70mol percent at the terminal of the prepared HRPIB, but the main defect of the technology is that BF is3In the gaseous state and thus difficult to handle, and harmful to the plant, and BF3The fluoride ion in the counter anion formed by the complex initiating system can also be transferred to the polyisobutene chain end to form a polyisobutenyl fluoride.
In recent years, with the improvement of the environmental protection technical standard of lubricating oil/fuel additive, some new HRPIB synthesis methods are emerging continuously: one is based on the living cationic polymerization end group quenching method to obtain HRPIB. Commonly used methods for end group quenching are: allyltrimethylsilane (ATMS)) end group quenching, hindered base end group quenching, and sulfide and ether end group quenching; another method is based on the conventional cationic polymerization method, which uses conventional metal halide and ether complexes as coinitiators for the cationic polymerization of isobutene. AlCl was used first3/R2O; subsequent FeCl3(GaCl3)/R2O was subsequently used for the synthesis of HRPIB. To improve AlCl3Solubility of the catalyst in nonpolar solvents, RAlCl2/R2The O catalytic systems are produced successively, by which a monofunctional, highly reactive polyisobutene is obtained.
Patent document 1 employs TiC14The co-initiation system is used to prepare high activity polyisobutene, and organic compound additive is introduced into the polymerization system to efficiently and selectively remove adjacent-CH of active chain terminal carbonium ions3the beta-H generates a polyisobutene chain end α -double bond structure, so that the high-activity polyisobutene with a single functional group is directly prepared, and the content of the chain end α -double bond can reach more than 90 percent.
Patent document 2 proposes a hydrocarbon mixture particularly suitable for isobutylene, isobutylene or a mixed light C containing isobutylene4A method for preparing high-activity polyisobutene by carbocationic polymerization of fractions. From TiC1 in the presence of alcohol, phenol and/or ether organic compounds4co-initiating isobutylene cationic polymerization, and regulating the amount and proportion of alcohol, phenol or ether and the steric hindrance of counter ion to obtain high activity polyisobutylene with single functional group and distribution index up to 1.2 and alpha-double bond content up to 90 mol% in the end of polyisobutylene chain.
Patent document 3 discloses the use of AlCl in a polymerization system of a liquid phase isobutylene raw material3and the catalyst and oxygen-containing organic compound form a complex catalyst to initiate isobutylene polymerization, and the monofunctional high-activity polyisobutylene with the chain end α -double bond content of more than 80 mol% and the number average molecular weight of 800-5000g/mol is directly obtained.
Patent document 4 discloses the use of FeCl3the complex with the organic compound containing oxygen or sulfur is used as an initiating system to directly obtain the monofunctional group high-activity polyisobutene with narrower molecular weight distribution and more than 75mol percent (even as high as 90mol percent) of content of terminal α -double bonds.
Documents of the prior art
Patent document
Patent document 1: CN201310042536.5
Patent document 2: CN201310041415.9
Patent document 3: CN200810115711.8
Patent document 4: CN200910089266.7
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a method for preparing high-activity polyisobutene by using a bifunctional initiator, wherein two ends of the prepared high-activity polyisobutene are respectively provided with exo-olefin terminal group groups, the structural content range of external olefins at the two ends is 70-99 mol%, the number average molecular weight of the high-activity polyisobutene is controllable, and the molecular weight distribution is narrow.
Means for solving the technical problem
Aiming at the problems, the invention provides a method for preparing high-activity polyisobutene by using bifunctional initiator, which takes isobutene as raw material and prepares the high-activity polyisobutene by cationic polymerization at low temperature, and comprises the following steps:
(1) the charging stage of the initiating system adopts one of the following two charging modes: firstly, adding a main initiator and a coinitiator into a polymerization reaction system, mixing and aging, and then adding a proton transfer agent; adding a co-initiator and a proton transfer agent into a polymerization reaction system, mixing, aging, and then adding a main initiator for aging;
(2) polymer reaction stage: adding isobutene into the polymerization reaction system for polymerization.
In one embodiment, the solvent used in the reaction system is a nonpolar solvent.
In one embodiment, the solvent used in the reaction system is selected from pentane, cyclopentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane, methylcyclohexane, and preferably n-hexane and cyclopentane.
One embodiment is one wherein the primary initiator is selected from the group consisting of 5-tert-butyl-bis (2-methoxy-2-propyl) benzene, 1, 3-bis (2-chloro-1-methylethyl) -5-tert-butylbenzene, 1, 3-bis (1-chloro-1-methyl-ethyl) -benzene, 1, 4-bis (1-chloro-1-methyl-ethyl) -benzene, at least one of 2-chloro-2-methylpropane, preferably 5-tert-butyl-bis (2-methoxy-2-propyl) benzene, 1, 3-bis (1-chloro-1-methyl-ethyl) -benzene, 1, 4-bis (1-chloro-1-methyl-ethyl) -benzene; the co-initiator is selected from at least one of Ethyl Aluminum Dichloride (EADC) and triethyl aluminum trichloride (EASC); the proton transfer agent is selected from 2, 2-dichlorodiethyl ether (CEE), diisopropyl ether (i-Pr)2O), di-sec-butyl ether (sec-Bu)2O), diisobutyl ether (i-Bu)2O), dibutyl ether (Bu)2O), tert-butyl methyl ether (t-BuOMe), butyl methyl ether (BuOMe), dibromodiethyl ether (DBE), bromomethyl ether (BMME), 3-bromopropyl methyl ether (BMP), 2-chloroethyl vinyl ether (2CVE), isopropyl-2-Bromoethyl Ether (BEPP), dichloroisopropyl ether (CIPE), chloromethyl methyl ether (DCMME), Chloromethyl Isopropyl Ether (CIE), preferably 2, 2-dichlorodiethyl ether.
In one embodiment, the concentration of the primary initiator is in the range of 1X 10-40.1mol/L, preferably 5X 10-3-0.01 mol/L; the molar ratio of coinitiator to main initiator ranges from 1 to 60, preferably from 1 to 20.
In one embodiment, the molar ratio of the coinitiator to the proton transferrer is in the range of 0.5 to 2, preferably 1 to 1.5.
In one embodiment, the monomer concentration of the isobutene is in the range from 0.5 to 8mol/L, preferably from 1 to 3 mol/L.
In one embodiment, the temperature of the initiation system feed stage and the polymer reaction stage is in the range of-30 ℃ to 10 ℃; the polymerization reaction time is 20-40 min.
According to a second aspect of the present invention there is provided a polyisobutene prepared according to the method of any one of the above.
One embodiment is one in which the content of exo-olefin terminal groups at both ends of the polyisobutylene is in the range of 70 to 99 mol%, the number average molecular weight of the polyisobutylene is in the range of 500 to 5000g/mol, and the molecular weight distribution is in the range of 1.5 to 3.0.
The invention has the advantages of
The bifunctional initiator is provided, under the temperature condition of minus 30 ℃ to 10 ℃, isobutene is used as a raw material, high-activity polyisobutene with exo-olefin terminal group groups at two ends is prepared through cationic polymerization, the number average molecular weight of the prepared high-activity polyisobutene is controllable, the number average molecular weight is 500 g/mol to 5000g/mol, the molecular weight distribution is narrow, the molecular weight distribution is 1.5 g/mol to 3.0 g/mol, the yield of the synthesized high-activity polyisobutene is high, the conversion rate of the isobutene is 60% to 100%, and the content range of the terminal exo-olefin structure is 70mol to 99 mol%.
Drawings
FIG. 1 is a GPC curve of HRPIB for the products of example 1, example 4, example 7, example 10, example 13, example 16.
FIG. 2 is a 1H NMR spectrum of HRPIB of the product synthesized in example 1.
FIG. 3 is a 1H NMR spectrum of HRPIB of the product synthesized in example 7.
FIG. 4 is a 1H NMR spectrum of HRPIB of the product synthesized in example 13.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto. The test modes are GPC and1H NMR。
examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples.
Example 1
Pumping cold liquid into a vacuum glove box, cooling to a polymerization temperature of 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding a main initiator of 0.005M, adding EADC of 0.02M, then uniformly mixing and aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and aging for 10min, finally adding a reaction terminator methanol to terminate the polymerization reaction after reacting for 20min, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 2
Pumping cold liquid into a vacuum glove box, cooling to a polymerization temperature of 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.04M of EADC, then uniformly mixing and aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1.5, uniformly mixing and aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 3
Pumping cold liquid into a vacuum glove box, cooling to a polymerization temperature of 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding a main initiator of 0.005M, adding EADC of 0.08M, then uniformly mixing and then aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and then aging for 10min, finally adding a reaction terminator methanol to terminate the polymerization reaction after reacting for 30min, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 4
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of 0 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.02M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 1M of an isobutene monomer, reacting for 20min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 5
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of 0 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.04M of EASC, adding CEE according to the proportion of 1:1 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 6
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of 0 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.08M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 3M of an isobutene monomer, reacting for 30min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 7
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.02M of EADC, then uniformly mixing and then aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and then aging for 10min, finally adding 1M of an isobutene monomer, reacting for 20min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 8
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.04M of EADC, then uniformly mixing and aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1.5, uniformly mixing and aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 9
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 10 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.08M of EADC, then uniformly mixing and then aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and then aging for 10min, finally adding 3M of an isobutene monomer, reacting for 30min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 10
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 10 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.02M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 1M of an isobutene monomer, reacting for 20min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 11
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of-20 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.04M of EASC, adding CEE according to the proportion of 1:1 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 12
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of-20 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.08M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 3M of an isobutene monomer, reacting for 30min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 13
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of-20 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.02M of EADC, then uniformly mixing and aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and aging for 10min, finally adding 1M of an isobutene monomer, reacting for 20min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 14
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of-20 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.04M of EADC, then uniformly mixing and aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1.5, uniformly mixing and aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 15
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 30 ℃, adding cyclohexane with the volume of 300ml into a precooled polymerization system, then adding 0.005M of a main initiator, adding 0.08M of EADC, then uniformly mixing and then aging for 10min, then adding CEE according to the proportion of a co-initiator and a proton transfer agent of 1:1, uniformly mixing and then aging for 10min, finally adding 3M of an isobutene monomer, reacting for 30min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at the temperature of 45 ℃ to constant weight.
Example 16
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 30 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.02M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 1M of an isobutene monomer, reacting for 20min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 17
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 30 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.04M of EASC, adding CEE according to the proportion of 1:1 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 2M of an isobutene monomer, reacting for 25min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Example 18
Pumping cold liquid into a vacuum glove box, cooling to the polymerization temperature of minus 30 ℃, adding 300ml of cyclopentane into a precooled polymerization system, then adding 0.08M of EASC, adding CEE according to the proportion of 1:1.5 of a co-initiator and a proton transfer agent, uniformly mixing, then aging for 10min, then adding 0.01M of a main initiator, uniformly mixing, then aging for 10min, finally adding 3M of an isobutene monomer, reacting for 30min, adding a reaction terminator methanol to terminate the polymerization reaction, repeatedly washing with hexane/methanol for three times after terminating the reaction, air-drying in a ventilation cabinet to remove the solvent, and vacuum-drying at 45 ℃ to constant weight.
Figure BDA0002382432140000121
Figure BDA0002382432140000131
Figure BDA0002382432140000141
Note: a is 5-tert-butyl-bis (2-methoxy-2-propyl) benzene, B is 3-bis (1-chloro-1-methyl-ethyl) -benzene, C is 1, 4-bis (1-chloro-1-methyl-ethyl) -benzene
Industrial applicability
The bifunctional initiator can be prepared at low cost, and the preparation method has the advantages of simple preparation process, good repeatability and easy realization of industrial production.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A method for preparing high-activity polyisobutylene by using bifunctional initiator, which takes isobutylene as raw material and prepares the high-activity polyisobutylene by cationic polymerization at low temperature, is characterized by comprising the following steps:
(1) the charging stage of the initiating system adopts one of the following two charging modes: firstly, adding a main initiator and a coinitiator into a polymerization reaction system, mixing and aging, and then adding a proton transfer agent; adding a co-initiator and a proton transfer agent into a polymerization reaction system, mixing, aging, and then adding a main initiator for aging;
(2) polymer reaction stage: adding isobutene into the polymerization reaction system for polymerization.
2. The process according to claim 1, wherein the solvent used in the reaction system is a nonpolar solvent.
3. The process according to claim 1 or 2, wherein the solvent used in the reaction system is selected from the group consisting of pentane, cyclopentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane, methylcyclohexane, preferably n-hexane and cyclopentane.
4. A process according to any one of claims 1 to 3, wherein the primary initiator is selected from the group consisting of 5-tert-butyl-bis (2-methoxy-2-propyl) benzene, 1, 3-bis (2-chloro-1-methylethyl) -5-tert-butylbenzene, 1, 3-bis (1-chloro-1-methyl-ethyl) -benzene, 1, 4-bis (1-chloro-1-methyl-ethyl) -benzene, at least one of 2-chloro-2-methylpropane, preferably 5-tert-butyl-bis (2-methoxy-2-propyl) benzene, 1, 3-bis (1-chloro-1-methyl-ethyl) -benzene, 1, 4-bis (1-chloro-1-methyl-ethyl) -benzene; the co-initiator is selected from at least one of Ethyl Aluminum Dichloride (EADC) and triethyl aluminum trichloride (EASC); the proton transfer agent is selected from 2, 2-dichlorodiethyl ether (CEE), diisopropyl ether (i-Pr)2O), di-sec-butyl ether (sec-Bu)2O), diisobutyl ether (i-Bu)2O), dibutyl ether (Bu)2O), tert-butyl methyl ether (t-BuOMe), butyl methyl ether (BuOMe), dibromoDiethyl ether (DBE), bromomethyl methyl ether (BMME), 3-bromopropyl methyl ether (BMP), 2-chloroethyl vinyl ether (2CVE), isopropyl-2-Bromoethyl Ether (BEPP), dichloroisopropyl ether (CIPE), chloromethyl methyl ether (DCMME), Chloromethyl Isopropyl Ether (CIE), preferably 2, 2-dichlorodiethyl ether.
5. The process of any of claims 1-4, wherein the concentration of the primary initiator ranges from 1 x 10-40.1mol/L, preferably 5X 10-3-0.01 mol/L; the molar ratio of coinitiator to main initiator ranges from 1 to 60, preferably from 1 to 20.
6. The process according to any one of claims 1 to 5, wherein the co-initiator to proton transfer agent molar ratio ranges from 0.5 to 2, preferably from 1 to 1.5.
7. The process according to any one of claims 1 to 6, wherein the isobutene has a monomer concentration in the range from 0.5 to 8mol/L, preferably from 1 to 3 mol/L.
8. The process of any one of claims 1 to 7, wherein the temperature of the initiation system feed stage and the polymer reaction stage is from-30 ℃ to 10 ℃; the polymerization reaction time is 20-40 min.
9. Polyisobutylene prepared according to the process of any one of claims 1-8.
10. Polyisobutylene according to claim 9, wherein the amount of exo-olefin end groups at both ends of the polyisobutylene is in the range of 70 to 99 mol%, the number average molecular weight of the polyisobutylene is in the range of 500 to 5000g/mol and the molecular weight distribution is in the range of 1.5 to 3.0.
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CN107118082A (en) * 2017-06-12 2017-09-01 北京石油化工学院 The preparation method of cationic polymerization bifunctional initiator and distant claw type polyisobutene
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CN102762610A (en) * 2010-02-17 2012-10-31 巴斯夫欧洲公司 Method for producing highly reactive isobutene homo or copolymers
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CN107118082A (en) * 2017-06-12 2017-09-01 北京石油化工学院 The preparation method of cationic polymerization bifunctional initiator and distant claw type polyisobutene
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