CN111393556A - Isomonoolefin-alkylstyrene copolymer and preparation method thereof - Google Patents
Isomonoolefin-alkylstyrene copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of an isomonoolefin-alkylstyrene copolymer, which is characterized in that isomonoolefin and alkylstyrene are used as polymerization monomers, alkylamine and/or aromatic amine are used as slurry stabilizers, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer. The invention takes Lewis acid as an initiator, and one or more slurry stabilizers are added into a reaction system, and the existence of the substances can reduce the reaction rate of cationic reaction, reduce product agglomeration so as to uniformly disperse the product, effectively improve the mass transfer and heat transfer of an isobutylene-alkylstyrene copolymer polymerization system, and ensure that a production device can run in a long period and a low load. Meanwhile, the quality of the product is more stable. The present invention provides an isomonoolefin-alkylstyrene copolymer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an isomonoolefin-alkylstyrene copolymer and a preparation method thereof.
Background
The isomonoolefin-alkylstyrene copolymer is a polymer obtained by cationic copolymerization of isomonoolefin and alkylstyrene at low temperature in a solvent by using Lewis acid as an initiator. Represented by isobutylene-alkylstyrene copolymers. Wherein, the content of the alkyl styrene is 2.5 percent to 5 percent, the butyl rubber has the basic performance of the butyl rubber and excellent ozone resistance, and is easy to further carry out chemical modification, and a bromination reaction is carried out to generate a vulcanizable benzyl bromide functional group. The brominated isobutylene-alkylstyrene copolymer has excellent air tightness and damping property of IIR, and also has heat resistance, ozone resistance and weather resistance superior to those of ethylene propylene diene monomer, and BIMS is used in tyre rubber material to improve dynamic performance, reduce rolling resistance and raise wet skid resistance. And has higher vulcanization activity, and can form a stable crosslinking system with various vulcanization systems. And simultaneously, the BIMS is easy to blend and modify with other polymers. Waddel et al reported that replacing styrene butadiene rubber in some tire tread compounds with BIMS significantly improved traction and reduced rolling resistance on winter and wet road surfaces.
The copolymerization of isobutylene and alkylstyrene is carried out by a carbocation reaction, and the reaction has the characteristics of high reaction rate, concentrated heat release and extremely low required reaction temperature. Meanwhile, slurry polymerization has the characteristics of easy gel hanging, easy agglomeration and the like, the polymerization temperature rise is accelerated due to the product agglomeration in the reaction process, the molecular weight of the product is sharply reduced, and the product quality is unstable. The control of the reaction rate, the rapid removal of the heat of polymerization to control the reaction at a constant low temperature, is a major problem in production.
Disclosure of Invention
The invention aims to provide an isobutylene-alkylstyrene copolymer and a preparation method thereof, and the preparation method can reduce the reaction rate of cationic reaction, reduce product agglomeration so as to uniformly disperse the product, effectively improve mass transfer and heat transfer of an isobutylene-alkylstyrene copolymer polymerization system, and enable a production device to operate in a long period and a low load.
The invention provides a preparation method of an isomonoolefin-alkylstyrene copolymer, which is characterized in that isomonoolefin and alkylstyrene are used as polymerization monomers, alkylamine and/or aromatic amine are used as slurry stabilizers, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer.
Preferably, the alkylamine is one or more of methylamine, ethylamine, tert-butylamine, dimethylamine, diethylamine and the like, and trimethylamine. (ii) a
The aromatic amine is aniline.
Preferably, the method specifically comprises the following steps:
A) mixing isomonoolefin, alkylstyrene and slurry stabilizer in a solvent to obtain a reactant solution;
B) mixing the reactant solution with an initiation system, and reacting to obtain isomonoolefin-alkylstyrene;
the initiation system is obtained by mixing a main initiator and an auxiliary initiator in a solvent and then aging at low temperature.
Preferably, the isomonoolefin is C4-C16;
the alkylstyrene is an alkylstyrene containing C1-C6 alkyl substituent at ortho-position, meta-position or para-position;
the molar ratio of the alkylstyrene to the isomonoolefin is (0.01-0.1): 1.
preferably, the mass content of the isomonoolefin in the reactant solution is 5-35 wt%;
the mass concentration of the slurry stabilizer in a polymerization system is 0.1-500 mg/Kg.
Preferably, the primary initiator is a lewis acid; the initiator aid is H2O or HCl;
the molar ratio of the main initiator to the isomonoolefin is (0.0001-0.005): 1;
the molar ratio of the main initiator to the auxiliary initiator is (1-10): 1.
preferably, the low-temperature aging temperature is-78 to-98 ℃, and the low-temperature aging time is 1 to 30 min.
Preferably, the reaction temperature in the step B) is-60 to-100 ℃, and the reaction time in the step B) is 1 to 30 min.
Preferably, in step a), the solvent is selected from one or more of methyl chloride, methylene chloride and n-hexane.
In step B), the solvent is selected from one or more of methyl chloride, dichloromethane and n-hexane.
The present invention provides an isomonoolefin-alkylstyrene copolymer obtained by the preparation method as described above.
The invention provides a preparation method of an isomonoolefin-alkylstyrene copolymer, which is characterized in that isomonoolefin and alkylstyrene are used as polymerization monomers, alkylamine and/or aromatic amine are used as slurry stabilizers, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer. The invention takes Lewis acid as an initiator, and one or more slurry stabilizers are added into a reaction system, and the existence of the substances can reduce the reaction rate of cationic reaction, reduce product agglomeration so as to uniformly disperse the product, effectively improve the mass transfer and heat transfer of an isobutylene-alkylstyrene copolymer polymerization system, and ensure that a production device can run in a long period and a low load. Meanwhile, the quality of the product is more stable.
Detailed Description
The invention provides a preparation method of an isomonoolefin-alkylstyrene copolymer, which is characterized in that isomonoolefin and alkylstyrene are used as polymerization monomers, alkylamine and/or aromatic amine are used as slurry stabilizers, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer.
Specifically, the preparation method comprises the following steps:
A) mixing isomonoolefin, alkylstyrene and slurry stabilizer in a solvent to obtain a reactant solution;
B) mixing the reactant solution with an initiation system, and reacting to obtain isomonoolefin-alkylstyrene;
the initiation system is obtained by mixing a main initiator and an auxiliary initiator in a solvent and then aging at low temperature.
In the present invention, the isomonoolefin is preferably an isomonoolefin having from C4 to C16, more preferably one or more of isobutylene, isopentene, isohexene, isoheptene, isooctene, isononyl, isodecene, isoundecene, isododecene, isotridecyl, isotetradecyl, isotentadecene and isocetylene, and in particular, in the embodiment of the present invention, isobutylene may be used; the alkylstyrene is preferably alkylstyrene containing C1-C6 alkyl substituent at ortho-position, meta-position or para-position, more preferably alkylstyrene containing C1-C6 alkyl substituent at para-position, and specifically, in the embodiment of the invention, the alkylstyrene can be p-methylstyrene; the slurry stabilizer is preferably an alkylamine, which is one or more of nitrogen-containing organic compounds such as methylamine, ethylamine, tert-butylamine, dimethylamine, diethylamine and the like, trimethylamine and the like, and/or an aromatic amine. (ii) a The aromatic amine is preferably aniline. The solvent is preferably one or more of monochloromethane, dichloromethane and n-hexane.
In the invention, the molar ratio of the alkyl styrene to the isomonoolefin is (0.01-0.1): 1, more preferably (0.02 to 0.08): 1, most preferably (0.03-0.06): 1, specifically, in the embodiment of the present invention, may be 0.02: 1. 0.025: 1 or 0.053: 1.
in the reactant solution obtained in the present invention, the mass concentration of the isomonoolefin is preferably 5 to 35%, more preferably 10 to 30%, and most preferably 15 to 25%, specifically, in the embodiment of the present invention, 10%, 15%, or 20%; the mass concentration of the slurry stabilizer in the reactant solution is preferably 0.1 to 500mg/Kg, more preferably 1 to 50mg/Kg, and most preferably 5 to 30mg/Kg, and specifically, in the embodiment of the present invention, may be 5.33mg/Kg, 16.65mg/Kg, or 8.68 mg/Kg.
In the present invention, the temperature of the mixing is preferably-50 to-95 deg.C, more preferably-60 to-90 deg.C, and most preferably-70 to-80 deg.C, and particularly, in the embodiment of the present invention, may be-80 deg.C, -85 deg.C, or-90 deg.C.
In the present invention, the primary initiator is preferably a lewis acid, more preferably one or more of aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, butylaluminum dichloride, dibutylaluminum monochloride, boron trifluoride, titanium tetrachloride-neutralized aluminum sesqui-chloride, most preferably ethylaluminum dichloride; the coinitiator is preferably H2O or HCl, and the molar ratio of the main initiator to the isomonoolefin is preferably (0.0001-0.005): 1, more preferably (0.0001 to 0.002): 1, more preferably (0.0005 to 0.001): 1, specifically, in the embodiments of the present invention, may be 0.001, 0.0005 or 0.00067; the molar ratio of the main initiator to the auxiliary initiator is preferably (1-10): 1, more preferably (2-10): 1, most preferably (5-10): 1, specifically, in embodiments of the present invention, may be 9.78, 9.97 or 7.52.
The invention preferably prepares the main initiator solution and the auxiliary initiator solution with certain concentration with the solvent respectively, and then mixes the solutions to obtain the initiation system. In the present invention, the solvent is preferably one or more of monochloromethane, dichloromethane and n-hexane; the mass concentration of the main initiator solution is preferably 10-60%, and more preferably 20-40%; the mass concentration of the co-initiator is preferably 0.01-0.1%, and more preferably 0.025-0.05%; the solvents used in the main initiator solution and the co-initiator solution may be the same or different, and the present invention is not particularly limited thereto.
In the present invention, the temperature of the low-temperature aging is preferably-78 to-98 ℃, preferably-88 to-95 ℃, more preferably-92 to-95 ℃, and particularly, in the embodiment of the present invention, may be-95 ℃, -98 ℃ or-97.5 ℃; the aging time is 1-30 min, preferably 5-30 min, more preferably 10-20 min, and specifically, in the embodiment of the present invention, the aging time may be 15min, 20min or 30 min.
After obtaining the initiation system, the invention adds the reactant solution into the initiation system to carry out polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer,
in the present invention, the reaction temperature is-60 to-100 ℃, preferably-80 to-98 ℃, more preferably-90 to-97.5 ℃, and specifically, in the embodiment of the present invention, may be-95 ℃, -98 ℃, or-97.5 ℃; the reaction time is 1-20 min, preferably 2-15 min, more preferably 5-10 min, and specifically, in the embodiment of the present invention, 10min or 20min may be used.
And after the reaction is finished, adding an alcohol compound into the product slurry to terminate the reaction, thereby obtaining a final product. The alcohol is one or more of methanol, ethanol, propanol, and glycerol. And finally, drying the product slurry in a vacuum oven to remove the solvent to obtain the product.
The invention also provides an isomonoolefin-alkylstyrene copolymer prepared by the preparation method, wherein the isomonoolefin-alkylstyrene copolymer has a molar content of p-methylstyrene of 1-10%, more preferably 3-6%, and most preferably 4-4.5%, specifically, in the embodiment of the invention, 3.9%, 4.5% or 5.2%; the number average molecular weight is preferably 200000 to 400000, more preferably 240000 to 350000, and specifically, in the embodiment of the present invention, 240000, 300000 or 350000; the molecular weight distribution is 1.5-3, more preferably 1.8-2.5, and specifically, in the embodiment of the present invention, it may be 1.8, 2.0 or 2.5.
The invention provides a preparation method of an isomonoolefin-alkylstyrene copolymer, which is characterized in that isomonoolefin and alkylstyrene are used as polymerization monomers, alkylamine and/or aromatic amine are used as slurry stabilizers, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer. The polymerization of isobutylene-alkylstyrene copolymer is typical of cationic polymerization, the reaction speed is fast, the heat release is not easy to control, and the molecular weight of the polymer is sharply reduced along with the increase of temperature, resulting in unstable product quality. The invention takes Lewis acid as an initiator, and one or more slurry stabilizers are added into a reaction system, and the existence of the substances can reduce the reaction rate of cationic reaction, reduce product agglomeration so as to uniformly disperse the product, effectively improve the mass transfer and heat transfer of an isobutylene-alkylstyrene copolymer polymerization system, and ensure that a production device can run in a long period and a low load. Meanwhile, the quality of the product is more stable.
In order to further illustrate the present invention, the following examples are given to describe in detail an isobutylene-alkylstyrene copolymer and a preparation method thereof, which should not be construed as limiting the scope of the present invention.
Example 1
At-85 deg.C, 15g of isobutylene was weighed into 135g of methyl chloride, and then 0.8g of p-methylstyrene was added and mixed uniformly to obtain a monomer solution.
0.01g of tert-butylamine was weighed and added to the monomer solution to obtain a reactant solution, which was cooled to-95 ℃.
0.17g of 20% dichloroethylaluminum/n-hexane solution is weighed and added into 4g of 0.025wt% HCl n-hexane solution to be uniformly mixed to obtain an initiation system, and the initiation system is aged for 30min at the temperature of minus 95 ℃.
Adding the initiating system into the reactant solution to react for 20min at the temperature of-95 ℃ to obtain product slurry.
The reaction was terminated by adding 2g of ethanol, and the slurry was put into a vacuum oven to remove the solvent to obtain an isobutylene-alkylstyrene copolymer in a yield of 92%.
The obtained isobutylene-alkylstyrene copolymer was subjected to nuclear magnetic resonance analysis and GPC test, and the molar content of p-methylstyrene in the obtained isobutylene-alkylstyrene copolymer was 4.5 mol%, the number average molecular weight was 350000, and the molecular weight distribution was 1.8.
Example 2
At-90 deg.C, 45g of isobutylene was weighed into 255g of methyl chloride, and then 5g of p-methylstyrene was added and mixed uniformly to obtain a monomer solution.
0.01g of dimethylamine was weighed and added to the monomer solution to obtain a reactant solution, and the solution was cooled to-95 ℃.
0.26g of 20% dichloroethylaluminum/n-hexane solution is weighed and added into 6g of 0.025wt% HCl dichloromethane solution to be uniformly mixed to obtain an initiation system, and the initiation system is aged for 20min at the temperature of minus 98 ℃.
Adding the initiating system into the reactant solution to react for 10min at the temperature of minus 98 ℃ to obtain product slurry.
The reaction was terminated by adding 5g of methanol, and the slurry was put into a vacuum oven to remove the solvent to obtain an isobutylene-alkylstyrene copolymer at a yield of 81%.
The isobutylene-alkylstyrene copolymer obtained by nuclear magnetic resonance analysis and GPC test had a p-methylstyrene content of 5.2 mol%, a number average molecular weight of 300000 and a molecular weight distribution of 2.0.
Example 3
50g of isobutylene was weighed at-80 ℃ and added to 200g of methyl chloride, and then 2.17g of p-methylstyrene was added and mixed uniformly to obtain a monomer solution.
0.025g of aniline was weighed into the monomer solution to obtain a reactant solution, which was cooled to-95 ℃.
0.188g of 40% ethyl aluminum dichloride/n-hexane solution is weighed and added into 5.75g of 0.05wt% HCl in dichloromethane to be uniformly mixed to obtain an initiating system, and the initiating system is aged for 15min at the temperature of minus 97.5 ℃.
Adding the initiating system into the reactant solution to react for 20min at the temperature of-97.5 ℃ to obtain product slurry.
The reaction was terminated by adding 2g of diethylene glycol, and the slurry was placed in a vacuum oven to remove the solvent to obtain an isobutylene-alkylstyrene copolymer in a yield of 77%.
The isobutylene-alkylstyrene copolymer obtained by nuclear magnetic resonance analysis and GPC test had a p-methylstyrene molar content of 3.9 mol%, a number average molecular weight of 240000 and a molecular weight distribution of 2.5.
Comparative example 1
The process flow and the steps are the same as those of the example 1, and the mixture ratio of other materials is also the same, except that no nitrogen-containing organic compound is added. The product is agglomerated and stuck on the stirring paddle and the kettle wall.
The product was agglomerated on the stirring paddle and the wall of the kettle, with a yield of 53%.
The above-mentioned product prepared in comparative example 1 was subjected to nuclear magnetic resonance analysis and GPC measurement, and the obtained isobutylene-alkylstyrene copolymer had a molar content of p-methylstyrene of 1.5 mol%, a number average molecular weight of 200000, and a molecular weight distribution of 3.0.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A process for preparing the isomonoolefin-alkylstyrene copolymer features that the isomonoolefin and alkylstyrene are used as polymerizing monomers, alkylamine and/or aromatic amine are used as slurry stabilizer, and the polymerization reaction is initiated by the trigger system consisting of main trigger and assistant trigger to obtain the isomonoolefin-alkylstyrene copolymer.
2. The method according to claim 1, wherein the alkylamine is one or more of methylamine, ethylamine, tert-butylamine, dimethylamine, diethylamine, etc. and trimethylamine;
the aromatic amine is aniline.
3. The preparation method according to claim 1, comprising the following steps:
A) mixing isomonoolefin, alkylstyrene and slurry stabilizer in a solvent to obtain a reactant solution;
B) mixing the reactant solution with an initiation system, and reacting to obtain isomonoolefin-alkylstyrene;
the initiation system is obtained by mixing a main initiator and an auxiliary initiator in a solvent and then aging at low temperature.
4. The process according to claim 3, wherein the isomonoolefin is a C4-C16 isomonoolefin;
the alkylstyrene is an alkylstyrene containing C1-C6 alkyl substituent at ortho-position, meta-position or para-position;
the molar ratio of the alkylstyrene to the isomonoolefin is (0.01-0.1): 1.
5. the preparation method according to claim 3, wherein the mass content of the isomonoolefin in the reactant solution is 5-35 wt%;
the mass concentration of the slurry stabilizer in a polymerization system is 0.1-500 mg/Kg.
6. The method of claim 3, wherein the primary initiator is a Lewis acid; the initiator aid is H2O or HCl;
the molar ratio of the main initiator to the isomonoolefin is (0.0001-0.005): 1;
the molar ratio of the main initiator to the auxiliary initiator is (1-10): 1.
7. the preparation method according to claim 3, wherein the temperature of the low-temperature aging is-78 to-98 ℃, and the time of the low-temperature aging is 1 to 30 min.
8. The method according to claim 3, wherein the reaction temperature in step B) is-60 to-100 ℃, and the reaction time in step B) is 1 to 30 min.
9. The method according to claim 3, wherein in step A), the solvent is selected from one or more of methyl chloride, methylene chloride and n-hexane;
in step B), the solvent is selected from one or more of methyl chloride, dichloromethane and n-hexane.
10. An isomonoolefin-alkylstyrene copolymer obtained by the preparation method according to any one of claims 1 to 8.
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