CN115521418A - Isoolefin copolymer and process for producing the same - Google Patents

Isoolefin copolymer and process for producing the same Download PDF

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CN115521418A
CN115521418A CN202110709587.3A CN202110709587A CN115521418A CN 115521418 A CN115521418 A CN 115521418A CN 202110709587 A CN202110709587 A CN 202110709587A CN 115521418 A CN115521418 A CN 115521418A
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isoolefin
molecular weight
copolymer
initiator solution
production method
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张雷
孟伟娟
邓征威
邱迎昕
但雪峰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths

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Abstract

The invention relates to the field of polymer preparation, and discloses a preparation method of an isoolefin copolymer and the isoolefin copolymer prepared by the method. The method comprises the following steps: under the condition of low-temperature cationic polymerization and in the presence of halogenated alkane, the initiator solution is in contact reaction with at least one isoolefin and at least one conjugated diene; the initiator solution includes at least one proton donating compound, at least one lewis acid, and at least one styrene containing polymer. The isoolefin copolymer prepared by the preparation method has high weight average molecular weight and wide molecular weight distribution, and the by-products are few and the chain transfer phenomenon is obviously reduced in the preparation process.

Description

Isoolefin copolymer and preparation method thereof
Technical Field
The invention relates to the field of polymer preparation, in particular to a preparation method of an isoolefin copolymer and the isoolefin copolymer prepared by the method.
Background
The isoolefin copolymer refers to a copolymer obtained by copolymerizing a C4-C7 isoolefin monomer and other monomers, wherein the common isoolefin copolymer is butyl rubber, and the butyl rubber has good air tightness and excellent comprehensive performance and is an important raw material in the tire industry. The industrial production usually adopts slurry polymerization or solution polymerization to produce butyl rubber, but the molecular weight distribution of the obtained butyl rubber is narrow.
One of the important problems associated with the slurry polymerization process for butyl rubber production is the processability of butyl rubber. It has been found through many years that the processability of butyl rubber is actually important in relation to the molecular weight distribution, and in the production of butyl rubber, in addition to ensuring a sufficient weight average molecular weight, it is necessary to maintain a proper balance of high and low molecular weight fractions, the high molecular weight fraction being used to obtain a sufficient green strength and the low molecular weight fraction being used to ensure a certain stress relaxation rate. The comparison shows that the butyl rubber with narrow molecular weight distribution is easy to break on a mixing roll, the problem of widening the molecular weight distribution can be solved, and the carbon black can be uniformly and finely dispersed without an extreme mixing step in the mixing process, so that the product has better physical and mechanical properties; butyl rubber with a broad molecular weight distribution also has a more stable size and shape during processing. However, the molecular weight distribution of a polymer before processing is greatly dependent on the polymerization mechanism, and the molecular weight distribution characteristics of the polymer have been determined by a definite reaction. Therefore, special methods or means are often required for the purpose of broadening the molecular weight distribution of the polymer.
With respect to methods for broadening the molecular weight distribution of butyl rubber or improving the processability of butyl rubber, US2781334A discloses introducing a coupling agent, divinylbenzene (DVB), into the polymerization system to couple a portion of the molecular chains to form a small amount of branched macromolecules with high molecular weight to increase the initial strength of the polymer. But excessive use of DVB can cause significant gelling problems. WO0216452A1 improves this process by introducing a chain transfer agent such as diisobutylene in a suitable amount with the addition of a multiolefin crosslinking agent such as DVB to improve the gelling problem and the processability of the polymer
CN1427851A provides a process for producing butyl rubber with wide molecular weight distribution, which synthesizes butyl rubber by using a mixed catalyst system at-100 to-50 ℃, wherein the mixed catalyst comprises ethyl aluminum dichloride, diethyl aluminum chloride and a small amount of aluminoxane.
US7893176B2 describes a process for controlling the molecular weight distribution of isoolefin polymers by means of additives which are substances containing oxygen molecules or organic oxygen-containing compounds (e.g. alcohols, ethers, ketones, aldehydes, esters) and in which systems lewis acids, initiators, diluents, etc. are also present. The molecular weight distribution of the obtained isoolefin copolymer is higher than 2.0.
CN100523018C provides a method for preparing an isoolefin polymer or copolymer, which comprises homopolymerizing a C4-C7 isoolefin monomer or copolymerizing the isoolefin monomer with other monomers in a halogenated hydrocarbon or hydrocarbon diluent in the presence of a composite catalyst solution, wherein the composite catalyst solution is a reaction product of lewis acid and an additive, and the additive is selected from at least one of alcohols, phenols, amides, amines, or pyridines, carboxylates, and ketones. The method can adjust the molecular weight distribution of the product within a certain range by adjusting the proportion of the additive to the aluminum trichloride.
The method for adding the additive has the defects of increasing by-products of the reaction, aggravating the chain transfer phenomenon and the like.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide an isoolefin copolymer and a method for preparing the same, which can produce an isoolefin copolymer having a high weight average molecular weight and a broad molecular weight distribution.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an isoolefin copolymer, comprising the steps of:
under the condition of low-temperature cationic polymerization and in the presence of halogenated hydrocarbon, the initiator solution is in contact reaction with at least one isoolefin and at least one conjugated diene;
the initiator solution includes at least one proton donating compound, at least one lewis acid, and at least one styrene containing polymer.
The second aspect of the present invention provides an isoolefin copolymer obtained by the above-mentioned production method.
Through the technical scheme, the preparation method of the isoolefin copolymer and the isoolefin copolymer prepared by the method provided by the invention have the following beneficial effects:
in the preparation method of the isoolefin copolymer provided by the invention, the styrene-containing polymer is introduced into a common initiation system, a part of isoolefin copolymer with a star-shaped branched structure can be obtained in the polymerization process, the part of isoolefin copolymer has high molecular weight so that the isoolefin copolymer has enough strength, and a conventional initiation system HCl/AlC is adopted 2 H 5 Cl 2 Isoolefin copolymers of linear structure can be obtained.
Furthermore, in the preparation method of the isoolefin copolymer provided by the invention, the isoolefin copolymer with different molecular weight distributions can be obtained by adjusting the ratio of HCl to the polymer containing styrene in the initiating system.
Furthermore, in the preparation method of the isoolefine copolymer, the obtained polymer particles are in a glass state by taking the fluoroalkane as the diluent, the operation period of a polymerization kettle can be obviously prolonged, and the polymerization reaction temperature can be increased by 10-20 ℃ compared with a methyl chloride system.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for producing an isoolefin copolymer, characterized in that the method comprises the steps of:
under the condition of low-temperature cationic polymerization and in the presence of halogenated hydrocarbon, the initiator solution is in contact reaction with at least one isoolefin and at least one conjugated diene;
the initiator solution includes at least one proton donating compound, at least one lewis acid, and at least one styrene containing polymer.
In the invention, in the preparation process of the isoolefin copolymer, the styrene-containing polymer is added into a conventional isoolefin copolymer initiating system, so that the molecular weight of the isoolefin copolymer can be obviously improved, and the isoolefin copolymer with wide distribution can be obtained.
According to the invention, the isoolefin has the structure shown in formula I:
Figure BDA0003132959790000041
wherein, in the formula I, R 1 Is C 1 -C 5 Alkyl or hydrogen of (a); r 2 Is C 1 -C 5 Alkyl or C of 3 -C 5 Branched alkyl groups of (a).
Further, in the formula I, R 1 Is C1-C4 alkyl; r is 2 Is C1-C4 alkyl.
Further, in formula I, R 1 Is methyl, R 2 Is a methyl group.
According to the invention, the styrene-containing polymer has the structure shown in formula II:
Figure BDA0003132959790000042
wherein n, m, a, b and h satisfy the following relationship: n: (m + a + b): h =1:0.1-1:1; b/(m + a + b) is more than or equal to 0 and less than or equal to 80 percent.
In the present invention, an initiator solution containing a styrene-containing polymer having the formula II is used to prepare an isoolefin copolymer, and since the content of each structural unit in the polymer satisfies the above-mentioned specific relationship, the copolymer can function as a grafting agent, and the 3,4-structure formed after polymerization of isoprene units in the copolymer can function as an initiator, thereby preparing an isoolefin copolymer having a high weight average molecular weight and a broad molecular weight distribution.
In the present invention, the content of each structural unit in the styrene-containing polymer is described in "synthesis of a butyl lithium-initiated styrene-isoprene-styrene triblock copolymer and a structural and performance table thereof [ J ] materials report, 2014, 10: 371'.
Further, n, m, a, b, and h satisfy the following relationship: n: (m + a + b): h =1:0.4-0.8:1; b/(m + a + b) is more than or equal to 5 percent and less than or equal to 80 percent.
Further, n, m, a, b, and h satisfy the following relationship: n: (m + a + b): h =1:0.5-0.7:1; when b/(m + a + b) ≦ 70%, the isoolefin copolymer thus produced can further broaden the molecular weight distribution of the isoolefin copolymer while maintaining a high weight average molecular weight.
According to the present invention, the weight average molecular weight of the styrene-containing polymer is 5,000 to 30,000; the molecular weight distribution is 1-3.
Further, the weight average molecular weight of the styrene-containing polymer is 10,000 to 100,000; the molecular weight distribution is 1-2.
In the present invention, the weight average molecular weight and the molecular weight distribution of the styrene-containing polymer were measured by LC-20A type liquid gel permeation chromatograph manufactured by Shimadzu corporation, japan.
In the present invention, the styrene-containing polymer is prepared by the following method:
the polymerization temperature is 40 ℃, the solvent is a mixed solvent, wherein 10ml of cyclohexane and 30 ml of tetrahydrofuran are adopted as the solvent, 1.8 ml of 0.1M butyl lithium heptane solution is added into the solvent, 4.2 ml of styrene is sequentially added, 1.5 ml of isoprene is added after 40 minutes of reaction, 4.2 ml of styrene is added after 50 minutes of reaction is continued, and methanol is used for termination after 40 minutes of reaction, thus preparing the styrene-containing polymer.
According to the invention, the conjugated diene is selected from isoprene and/or butadiene, preferably isoprene.
According to the invention, the concentration of the proton-donating compound is from 0.001 to 0.1mol/L, based on the total weight of the initiator solution.
In the present invention, the proton-donating compound is preferably introduced into the polymerization system in the form of a solution, and the solvent used to prepare the solution of the proton-donating compound is selected from dichloromethane and/or monochloromethane.
Further, the concentration of the proton-donating compound is 0.001 to 0.05mol/L based on the total weight of the initiator solution.
According to the invention, the proton-providing compound is selected from water and/or HCl.
According to the invention, the concentration of the Lewis acid is 0.0001 to 0.1mol/L, based on the total weight of the initiator solution.
In the present invention, the Lewis acid is preferably introduced into the polymerization system in the form of a solution, and the solvent used for preparing the solution of the Lewis acid is at least one selected from the group consisting of heptane, n-hexane and n-pentane.
Further, the concentration of the Lewis acid is 0.01-0.1mol/L based on the total weight of the initiator solution.
According to the invention, the Lewis acid is selected from at least one of aluminum trichloride, titanium tetrachloride, boron trifluoride and ethyl aluminum dichloride; preferably ethyl aluminium dichloride.
According to the invention, the concentration of the styrene-containing polymer is from 0.0001 to 0.01mol/L, based on the total weight of the initiator solution.
In the present invention, the styrene-containing polymer is preferably introduced into the polymerization system in the form of a solution, and the solvent used for preparing the solution of the styrene-containing polymer is selected from dichloromethane and/or chloroform.
Further, the concentration of the styrene-containing polymer is 0.001 to 0.005mol/L based on the total weight of the initiator solution.
In the present invention, isoolefin copolymers having different molecular weight distributions can be obtained by adjusting the amount ratio of the proton-donating compound to the styrene-containing polymer, and particularly, in one embodiment of the present invention, the amount ratio of the proton-donating compound to the styrene-containing polymer is 10-1:1-100.
According to the invention, the halogenated alkane is a fluorinated alkane.
In the invention, halogenated alkane, especially fluorinated alkane is used as a diluent for the copolymerization of isoolefin, so that the prepared polymer is in a glass state, the operation period of a polymerization kettle can be obviously prolonged, and the polymerization temperature can be increased by 10-20 ℃ compared with a chloromethane system.
Further, the halogenated alkane is selected from at least one of 1, 1-difluoroethane, 1-trifluoroethane and 1, 2-tetrafluoroethane.
According to the present invention, the low temperature cationic polymerization conditions include: the polymerization temperature is-40 ℃ to 100 ℃, and the polymerization time is 1-30min.
Further, the low temperature cationic polymerization reaction conditions include: the polymerization temperature is-40 ℃ to 100 ℃, and the polymerization time is 0.5 min to 15min.
According to the invention, the amount of isoolefin is 90-99wt% based on the total weight of isoolefin and conjugated diene; the amount of the conjugated diene is 1 to 10wt%.
Further, the amount of the isoolefin is 95-98wt% based on the total weight of the isoolefin and the conjugated diene; the amount of the conjugated diene is 2-5wt%.
According to the invention, the halogenated alkane is used in an amount of 100 to 1000 parts by weight, based on 100 parts by weight of isoolefin and conjugated diene; the initiator solution is used in an amount of 0.01 to 5 parts by weight.
Further, the halogenated alkane is used in an amount of 400 to 800 parts by weight based on 100 parts by weight of isoolefin and conjugated diene; the initiator solution is used in an amount of 0.1 to 1 part by weight.
In the present invention, the method further comprises adding a terminator to the polymerization system to terminate the polymerization reaction.
Preferably, the terminator is selected from at least one of methanol, ethanol, butanol, and tert-butanol. The amount of the terminator can be adjusted according to the actual needs, for example, the amount of the terminator is 1 to 5wt% of the total amount of the isoolefin and the conjugated diene.
In the present invention, the method further comprises a step of removing unreacted monomers and solvent, specifically: the polymer solution obtained by the reaction was mixed with an equal volume of water, and unreacted monomers and solvent were removed at 100 ℃.
In a second aspect, the present invention provides an isoolefin copolymer prepared by the above process.
According to the invention, the isoolefin copolymer has a weight average molecular weight of from 200,000 to 1,000,000; the isoolefin copolymer has a molecular weight distribution greater than 3.
In the present invention, the weight average molecular weight and molecular weight distribution of the isoolefin copolymer are measured by LC-20A liquid gel permeation chromatography, manufactured by Shimadzu corporation, japan.
Further, the isoolefin copolymer has a weight average molecular weight of 400,000 to 800,000; the isoolefin copolymer has a molecular weight distribution of 3.6 to 5.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the conversion of monomer was measured by a weighing method.
Conversion (%) = (weight of obtained polymer/total weight of monomer added) × 100%; wherein the conversion of isobutylene is obtained after homopolymerization of isobutylene and the conversion of styrene is obtained after homopolymerization of styrene.
The molecular weight and molecular weight distribution of the polymer are determined by LC-20A liquid gel permeation chromatograph manufactured by Shimadzu corporation of Japan, and single-pore chromatographic column
Figure BDA0003132959790000081
And
Figure BDA0003132959790000082
the four columns are used together. The mobile phase is tetrahydrofuran, and the flow rate is 0.7mL/min; the concentration of the sample solution is 2mg/mL, and the sample injection amount is 200 mu L; the test temperature is 35 ℃; single distribution polystyrene was used as a standard.
For the content of each structural unit in the styrene-containing polymer, reference is made to "synthesis of a butyl lithium-initiated styrene-isoprene-styrene triblock copolymer and a structural and performance table thereof [ J ] material report, 2014, 10:371", the solvents and monomers used were purified by methods commonly used in the art before use, and the polymerization and initiator solutions were prepared in a dry box commercially available from MBRAUN, germany, equipped with a low temperature cold bath.
Preparation example 1
The polymerization temperature was 40 ℃, the solvent was a mixed solvent, wherein cyclohexane was 10ml, tetrahydrofuran was 1 ml, then 1.8 ml of a 0.1M butyl lithium solution in heptane was added to the solvent, then styrene was sequentially added in an amount of 4.2 ml, 1.5 ml of isoprene was added after 40 minutes of reaction, and after 50 minutes of further reaction, styrene was added in an amount of 4.2 ml, and after 40 minutes of further reaction, termination was performed with methanol to prepare the styrene-containing polymer, designated as polymer A1, which was determined to have Mw =26,500, mwd =1.62, b/(M + a + b) =26%, n: (m + a + b): h =1:0.6:1.
preparation example 2
Styrene-containing polymer A2 was prepared by the method of preparation 1, except that: the amount of tetrahydrofuran added was 2 ml, and it was determined that the Mw =30,200, mwd =1.35, b/(m + a + b) =40%, n: (m + a + b): h =1:0.6:1.
preparation example 3
Styrene-containing polymer A3 was prepared by the method of preparation 1, except that: the amount of tetrahydrofuran added was 3 ml, and the Mw =31,200, mwd of polymer A3 was determined to be 1.24, b/(m + a + b) =60%, n: (m + a + b): h =1:0.6:1.
example 1
(1) Preparation of initiator solution
First, 0.36 g of polymer A1 was dissolved in 60 g of methylene chloride;
60 g of methylene chloride were weighed out and 4 ml of a 0.9mol/L heptane solution of ethyl aluminum dichloride, 10ml of a methylene chloride solution containing hydrogen chloride (concentration of hydrogen chloride is 0.1 mol/L) and 10ml of the above-mentioned polymer A1 solution were added in this order. Wherein the concentration of the polymer A1 is 0.005mol/L, the concentration of the hydrogen chloride is 0.01mol/L, and the concentration of the ethyl aluminum dichloride is 0.04mol/L based on the total weight of the initiator solution. The ratio of hydrogen chloride to polymer A1 used was 1:1.
(2) Polymerisation reaction
Under the protection of nitrogen, 100mL of 1, 1-difluoroethane precooled to minus 80 ℃ is sequentially added into a three-neck flask with stirring slurry in a cooling bath at minus 95 ℃, 16.8g of isobutene is added into the three-neck flask, the mixture is stirred for polymerization, 10mL of the prepared initiator solution is slowly dripped for initiating polymerization, the temperature of a polymerization system is kept at minus 90 +/-2 ℃,5 mL of methanol is added for termination after 30 minutes of polymerization, the polymer solution obtained after termination is poured into a beaker and injected with clean water with the same volume, the beaker is placed in a constant temperature water bath for removing unreacted monomers and solvents at 100 ℃, the polymer solution is naturally air-dried after being washed for three times, and the polymer P1 is prepared after being placed in a vacuum oven and dried to constant weight. The weight average molecular weight and molecular weight distribution of the copolymer P1 are shown in table 1.
Example 2
(1) Preparation of initiator solution
First, 0.36 g of polymer A1 was dissolved in 60 g of methylene chloride;
60 g of methylene chloride were weighed out and 4 ml of a 0.9mol/L heptane solution of ethyl aluminum dichloride, 10ml of a methylene chloride solution containing hydrogen chloride (concentration of hydrogen chloride is 0.1 mol/L) and 20 ml of the above polymer A1 solution were added in this order. Based on the total weight of the initiator solution, the concentration of the polymer A1 is 0.01mol/L, the concentration of hydrogen chloride is 0.01mol/L, and the concentration of ethyl aluminum dichloride is 0.04mol/L. The ratio of the amount of hydrogen chloride to the amount of polymer A1 was 1:2.
(2) Polymerisation reaction
Under the protection of nitrogen, 100mL of 1, 1-trifluoroethane precooled to-80 ℃ is sequentially added into a three-neck flask with stirring slurry placed in a cooling bath at-95 ℃, 16.8g of isobutene is added into the three-neck flask, the mixture is stirred for polymerization, 10mL of the prepared initiator solution is slowly dripped to initiate polymerization, the temperature of a polymerization system is kept at-90 +/-2 ℃,5 mL of methanol is added into the polymerization system for termination after 30 minutes of polymerization, the polymer solution obtained after termination is poured into a beaker and injected with clean water with the same volume, the polymer solution is placed in a constant temperature water bath to remove unreacted monomers and solvents at 100 ℃, the polymer solution is naturally air-dried after being washed for three times, and the polymer P2 is prepared after being placed in a vacuum oven and dried to constant weight. The weight average molecular weight and the molecular weight distribution of the copolymer P2 are shown in Table 1.
Example 3
(1) Preparation of initiator solution
First, 0.36 g of polymer A1 was dissolved in 60 g of methylene chloride;
60 g of methylene chloride were weighed out and 4 ml of a 0.9mol/L heptane solution of ethyl aluminum dichloride, 10ml of a methylene chloride solution containing hydrogen chloride (concentration of hydrogen chloride is 0.1 mol/L) and 5 ml of the above polymer A1 solution were successively added. Wherein the concentration of the polymer A1 is 0.005mol/L, the concentration of the hydrogen chloride is 0.01mol/L, and the concentration of the ethyl aluminum dichloride is 0.04mol/L based on the total weight of the initiator solution. The ratio of hydrogen chloride to polymer A1 used was 1:0.5.
(2) Polymerisation reaction
Under the protection of nitrogen, sequentially adding 100mL of 1, 2-tetrafluoroethane precooled to minus 80 ℃ into a three-neck flask with stirring slurry in a cooling bath at the temperature of minus 95 ℃, adding 16.8g of isobutene into the three-neck flask, carrying out polymerization reaction under stirring, slowly dropwise adding 10mL of the prepared initiator solution to initiate polymerization, keeping the temperature of a polymerization system at minus 90 +/-2 ℃, adding 5 mL of methanol into the flask after 30 minutes of polymerization reaction for termination, pouring the polymer solution obtained after termination into a beaker, injecting clean water with the same volume, placing the beaker in a constant-temperature water bath to remove unreacted monomers and solvents at the temperature of 100 ℃, washing the beaker with water for three times, naturally drying the beaker, and placing the beaker into a vacuum oven to dry the beaker to constant weight to obtain the copolymer P3. The weight average molecular weight and the molecular weight distribution of the copolymer P3 are shown in Table 1.
Example 4
An isoolefin copolymer was prepared by following the procedure of example 1, except that polymer A2 was used instead of polymer A1. A copolymer P4 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer P4 are shown in Table 1.
Example 5
An isoolefin copolymer was prepared by following the procedure of example 1, except that polymer A3 was used instead of polymer A1. A copolymer P5 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer P5 are shown in Table 1.
Example 6
An isoolefin copolymer was prepared by following the procedure of example 1, except that methyl chloride was used instead of 1, 1-difluoroethane. A copolymer P6 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer P6 are shown in Table 1.
Example 7
An isoolefin copolymer was prepared according to the method of example 1, except that: in the initiator solution, the concentration of the compound which donates protons was 0.06mol/L, the concentration of the styrene-containing polymer was 0.0005mol/L, and the concentration of the Lewis acid was 0.005mol/L. A copolymer P7 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer P7 are shown in table 1.
Example 8
An isoolefin copolymer was prepared according to the method of example 1, except that: in the initiator solution, the concentration of the proton-donating compound was 0.08mol/L, the concentration of the styrene-containing polymer was 0.0007mol/L, and the concentration of the Lewis acid was 0.006mol/L. A copolymer P8 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer P8 are shown in Table 1.
Comparative example 1
An isoolefin copolymer was prepared according to the procedure of example 1, except that low molecular weight polybutadiene was used instead of polymer A1. A copolymer D1 was obtained. The weight average molecular weight and the molecular weight distribution of the copolymer D1 were determined as shown in Table 1.
TABLE 1
Example numbering Weight average molecular weight Molecular weight distribution
Example 1 466,800 3.89
Example 2 524,000 4.25
Example 3 624,600 3.67
Example 4 386,900 3.82
Example 5 360,300 4.22
Example 6 523,600 3.75
Example 7 365,400 3.98
Example 8 389,500 3.68
Comparative example 1 524,200 3.52
It can be seen from the results in table 1 that the isoolefin copolymers obtained in examples 1-10 by the method of the present invention have significantly improved molecular weight distribution while maintaining a high weight average molecular weight.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A method for preparing an isoolefin copolymer, comprising the steps of:
under the condition of low-temperature cationic polymerization and in the presence of halogenated alkane, the initiator solution is in contact reaction with at least one isoolefin and at least one conjugated diene;
the initiator solution includes at least one proton donating compound, at least one lewis acid, and at least one styrene containing polymer.
2. The method of claim 1, wherein the isoolefin has the structure of formula I:
Figure FDA0003132959780000011
wherein R is 1 Is C 1 -C 5 Alkyl or hydrogen of (a); r 2 Is C 1 -C 5 Alkyl or C 3 -C 5 Branched alkyl groups of (a).
3. The production method according to claim 1 or 2, wherein the styrene-containing polymer has a structure represented by formula II:
Figure FDA0003132959780000012
wherein n, m, a, b and h satisfy the following relationship: n: (m + a + b): h =1:0.1-1:1; b/(m + a + b) is more than or equal to 0 and less than or equal to 80 percent;
preferably, n, m, a, b and h satisfy the following relationship: n: (m + a + b): h =1: 0.4-0.8; b/(m + a + b) is more than or equal to 5 percent and less than or equal to 80 percent.
4. The production method according to any one of claims 1 to 3, wherein the weight average molecular weight of the styrene-containing polymer is 5,000 to 30,000; the molecular weight distribution is 1-3.
5. The production method according to any one of claims 1 to 4, wherein the conjugated diene is selected from isoprene and/or butadiene.
6. The production method according to any one of claims 1 to 5, wherein the concentration of the proton-providing compound is 0.001 to 0.1mol/L based on the total weight of the initiator solution;
preferably, the proton donating compound is selected from water and/or HCl.
7. The production method according to any one of claims 1 to 6, wherein the concentration of the Lewis acid is 0.0001 to 0.1mol/L based on the total weight of the initiator solution;
preferably, the lewis acid is selected from at least one of aluminum trichloride, titanium tetrachloride, boron trifluoride and ethyl aluminum dichloride; preferably ethyl aluminium dichloride.
8. The production method according to any one of claims 1 to 7, wherein the concentration of the styrene-containing polymer is 0.0001 to 0.01mol/L, preferably 0.001 to 0.005mol/L, based on the total weight of the initiator solution.
9. The production method according to any one of claims 1 to 8, wherein the halogenated alkane is a fluorinated alkane, preferably at least one selected from the group consisting of 1, 1-difluoroethane, 1-trifluoroethane and 1, 2-tetrafluoroethane.
10. The production method according to any one of claims 1 to 9, wherein the low-temperature cationic polymerization reaction conditions include: the polymerization temperature is-40 ℃ to 100 ℃, and the polymerization time is 1-30min.
11. The production process according to any one of claims 1 to 10, wherein the isoolefin is used in an amount of 90 to 99% by weight based on the total weight of the isoolefin and the conjugated diene; the dosage of the conjugated diene is 1-10wt%;
preferably, the halogenated alkane is used in an amount of 100 to 1000 parts by weight, based on 100 parts by weight of the isoolefin and the conjugated diene; the initiator solution is used in an amount of 0.01 to 5 parts by weight.
12. An isoolefin copolymer produced by the production method according to any one of claims 1 to 11.
13. The isoolefin copolymer of claim 12, wherein the isoolefin copolymer has a weight average molecular weight of 200,000 to 1,000,000; the isoolefin copolymer has a molecular weight distribution greater than 3;
preferably, the weight average molecular weight of the isoolefin copolymer is 400,000 to 800,000; the isoolefin copolymer has a molecular weight distribution of 3.6 to 5.
CN202110709587.3A 2021-06-25 2021-06-25 Isoolefin copolymer and process for producing the same Pending CN115521418A (en)

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