CN111393556B - 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 products, effectively improve the mass transfer and heat transfer of an isobutylene-alkylstyrene copolymer polymerization system, and ensure that a production device can operate 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 a tire rubber material in combination, so that the dynamic property can be improved, the rolling resistance is reduced, and the wet skid resistance is improved. 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. Waddell 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, t-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 a 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 a C4 to 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 alkyl styrene to the isomonoolefin is (0.01-0.1): 1.
preferably, the mass content of the isomonoolefin in the reactant solution is 5 to 35wt%;
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 H 2 O 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 temperature of the low-temperature ageing is-78 to-98 ℃, and the time of the low-temperature ageing is 1 to 30min.
Preferably, the reaction temperature in the step B) is-60 to-100 ℃, and the reaction time in the step B) is 1 to 30min.
Preferably, in step a), the solvent is selected from one or more of methyl chloride, dichloromethane 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 process 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 a C4 to C16 isomonoolefin, more preferably one or more of isobutylene, isopentene, isohexene, isoheptene, isooctene, isononyl, isodecene, isoundecene, isododecene, isotridecyl, isotetradecyl, isotentadecene, and isocetylene, and in particular, in an embodiment of the present invention, isobutylene may be used; the alkylstyrene is preferably an alkylstyrene having an alkyl substituent of C1 to C6 at the ortho, meta or para position, more preferably an alkylstyrene having an alkyl substituent of C1 to C6 at the para position, and particularly, in the embodiment of the present invention, may be para-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 present invention, the molar ratio of the alkylstyrene to the isomonoolefin is (0.01 to 0.1): 1, more preferably (0.02 to 0.08): 1, most preferably (0.03 to 0.06): specifically, in the embodiment of the present invention, the ratio of 0.02: 1. 0.025:1 or 0.053:1.
the mass concentration of the isomonoolefin in the reactant solution obtained in the present invention is preferably 5 to 35%, more preferably 10 to 30%, most preferably 15 to 25%, and specifically, in the embodiment of the present invention, may be 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 8.68mg/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 main initiator is preferably a Lewis acid, and more preferably neutralized with aluminum trichloride, ethylaluminum dichloride, diethylaluminum monochloride, butylaluminum dichloride, dibutylaluminum monochloride, boron trifluoride and titanium tetrachlorideOne or more of a half aluminum, most preferably ethyl aluminum dichloride; the coinitiator is preferably H 2 O or HCl, preferably the molar ratio of the primary initiator to the isomonoolefin is (0.0001 to 0.005): 1, more preferably (0.0001 to 0.002): 1, more preferably (0.0005 to 0.001): 1, specifically, in embodiments of the present invention, may be 0.001, 0.0005 or 0.00067; the molar ratio of the main initiator to the co-initiator is preferably (1-10): 1, more preferably (2 to 10): 1, most preferably (5 to 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 to 60%, and more preferably 20 to 40%; the mass concentration of the co-initiator is preferably 0.01 to 0.1%, more preferably 0.025 to 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 low-temperature aging temperature is preferably-78 to-98 ℃, preferably-88 to-95 ℃, more preferably-92 to-95 ℃, and specifically, in the embodiment of the present invention, it may be-95 ℃, -98 ℃, or-97.5 ℃; the aging time is 1 to 30min, preferably 5 to 30min, more preferably 10 to 20min, and specifically, in the embodiment of the present invention, 15min, 20min or 30min may be used.
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, it may be-95 ℃, -98 ℃, or-97.5 ℃; the reaction time is 1 to 20min, preferably 2 to 15min, more preferably 5 to 10min, and specifically, in the embodiment of the present invention, may be 10min or 20min.
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, glycerol, etc. Finally, the product slurry is dried in a vacuum oven to remove the solvent, and the product is obtained.
The present invention also provides an isomonoolefin-alkylstyrene copolymer prepared according to the above-mentioned preparation method, wherein the isomonoolefin-alkylstyrene copolymer of the present invention has a molar content of p-methylstyrene of 1 to 10%, more preferably 3 to 6%, most preferably 4 to 4.5%, and specifically, in the embodiments of the present 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 to 3, more preferably 1.8 to 2.5, and specifically, in the embodiment of the present invention, 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 copolymers is typically a cationic polymerization, the reaction speed is fast, the exotherm is not easy to control, and the molecular weight of the polymer decreases sharply with increasing 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 ℃.
Weighing 0.17g of 20% dichloroethylaluminum/n-hexane solution, adding to 4g of 0.025wt% HCl in n-hexane solution, mixing well to obtain an initiation system, and aging at-95 ℃ for 30min.
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 isobutylene-alkylstyrene copolymer obtained by subjecting the isobutylene-alkylstyrene copolymer to nuclear magnetic resonance analysis and GPC test had a p-methylstyrene content of 4.5% by mol, a number average molecular weight of 350000 and a molecular weight distribution of 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 a 20% ethyl aluminum dichloride/n-hexane solution was weighed, added to 6g of a 0.025wt% HCl in methylene chloride solution, and mixed uniformly to obtain an initiation system, which was aged at-98 ℃ for 20min.
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 subjecting the isobutylene-alkylstyrene copolymer to nuclear magnetic resonance analysis and GPC test had a p-methylstyrene content of 5.2% by 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 ℃.
Weighing 0.188g of 40% ethyl aluminum dichloride/n-hexane solution, adding to 5.75g of 0.05wt% HCl in dichloromethane solution, mixing well to obtain the initiation system, aging at-97.5 deg.C for 15min.
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 is subjected to nuclear magnetic resonance analysis, GPC test, and the molar content of p-methylstyrene in the isobutylene-alkylstyrene copolymer obtained is 3.9% by mol, number average molecular weight 240000, molecular weight distribution 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 agglomerates 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 test, and the resulting isobutylene-alkylstyrene copolymer had a p-methylstyrene content of 1.5% by 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of isomonoolefin-alkylstyrene copolymer is characterized in that isobutylene and p-methylstyrene are used as polymerization monomers, alkylamine is used as a slurry stabilizer, and an initiation system consisting of a main initiator and an auxiliary initiator initiates polymerization reaction to obtain the isomonoolefin-alkylstyrene copolymer; the molecular weight distribution of the isomonoolefin-alkylstyrene copolymer is 1.8-2.5;
the main initiator is Lewis acid; the co-initiator is H 2 O or HCl;
the alkylamine is one or more of methylamine, ethylamine, tert-butylamine, dimethylamine, diethylamine and trimethylamine.
2. The preparation method according to claim 1, comprising the following steps:
a) Mixing isobutene, p-methylstyrene and a 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.
3. The process according to claim 2, wherein the molar ratio of p-methylstyrene to isobutylene is (0.01 to 0.1): 1.
4. the method according to claim 2, wherein the isobutylene is contained in the reactant solution in an amount of 5 to 35wt%;
the mass concentration of the slurry stabilizer in a polymerization system is 0.1-500 mg/Kg.
5. The method according to claim 2, wherein the molar ratio of the main initiator to isobutylene is (0.0001 to 0.005): 1;
the molar ratio of the main initiator to the auxiliary initiator is (1-10): 1.
6. the preparation method according to claim 2, wherein the temperature of the low-temperature aging is-78 to-98 ℃, and the time of the low-temperature aging is 1 to 30min.
7. The method according to claim 2, wherein the reaction temperature in step B) is-60 to-100 ℃, and the reaction time in step B) is 1 to 30min.
8. The method according to claim 2, 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.
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