CN106928391B - Preparation method of isobutylene, isoprene and alkylstyrene polymer - Google Patents
Preparation method of isobutylene, isoprene and alkylstyrene polymer Download PDFInfo
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- CN106928391B CN106928391B CN201511021343.7A CN201511021343A CN106928391B CN 106928391 B CN106928391 B CN 106928391B CN 201511021343 A CN201511021343 A CN 201511021343A CN 106928391 B CN106928391 B CN 106928391B
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Abstract
The invention provides a preparation method of a polymer of isobutene, isoprene and alkylstyrene, which comprises the steps of replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-50 to-100 ℃, adding methyl chloride as a solvent, adding an ionic liquid solution of the isobutene, the isoprene and the alkylstyrene, stirring for 10 to 30min, adding aniline, adding an initiator for 3 to 5 times, reacting for 30min to 3h, adding a terminator to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The polymer has good flexibility and good rigidity, so that the polymer has excellent processing performance and damping performance.
Description
Technical Field
The invention relates to a preparation method of a polymer of isobutene, isoprene and alkylstyrene, in particular to a method for preparing the polymer of the isobutene, the isoprene and the alkylstyrene by using a solution method.
Background
When the rubber material is in a glass transition region, the chain segment movement of the rubber material cannot completely follow the vibration speed, so that the rubber material generates friction in a molecular chain to absorb partial vibration energy and then dissipates in a heat energy form to effectively realize the purposes of vibration reduction and noise reduction. With the development of the automobile industry and the aerospace industry, the problems of automobile noise vibration, riding comfort and noise elimination and damping are more and more concerned by people, rubber is used as a novel functional material which can convert vibration energy and sound energy into heat energy to be consumed, and a vibration reduction and damping material becomes a research hotspot.
CN201410078284.6 relates to a preparation method of poly (isobutylene-co-p-methylstyrene) random copolymer, which adopts piperidine as a third component and alkyl aluminum as an initiator to successfully synthesize the poly (isobutylene-co-p-methylstyrene) random copolymer through positive ion copolymerization; has better molecular weight and molecular weight distribution. A method for synthesizing a poly (isobutylene-co-p-methylstyrene) random copolymer is provided, which is suitable for preparing the poly (isobutylene-co-p-methylstyrene) random copolymer by a slurry method and a solution method. CN 201010514252.8A method for preparing isoolefin copolymer; in halogenated hydrocarbon, hydrocarbon compound or their mixture, under the action of catalyst, making isoolefine monomer, multiolefine monomer and optional other copolymerizable monomer undergo the polymerization reaction, the described catalyst is the mixture of ethyl aluminium sesquichloride and water; the method for synthesizing the isoolefin copolymer by the environment-friendly and efficient solution method can solve the problem of low yield of the butyl rubber product by the solution method, simultaneously prolongs the continuous polymerization time of the reaction kettle, reduces the cleaning times, carries out polymerization at the relatively economic polymerization temperature of (-20 to-80 ℃), and is beneficial to energy conservation; saturated alkane is adopted as a solvent to replace methyl chloride used in a slurry method, which is beneficial to environmental protection. The preparation method of the CN201310546657.3 butyl rubber comprises the following steps: the raw material is prepared from isobutene and isoprene; polymerization: adding the raw materials into a polymerization kettle, then sequentially adding the catalyst and the diluent, and finally carrying out polymerization reaction for 2-4 hours at the temperature of-10 to-25 ℃ and under the condition of 1-14 KPa; and (4) terminating: adding isopropanol as a terminator after polymerization reaction, carrying out flash evaporation on the obtained polymer to remove unreacted monomers and solvents, and carrying out dehydration, extrusion, drying and briquetting to obtain a finished product of the butyl rubber. CN201310056027.8 a process for preparing a halogenated butyl elastomer graft copolymer, comprising: mixing a solution of a halobutyl elastomer with a phase transfer catalyst in the presence of a solution of an alkali metal salt of an oxygen or sulfur nucleophile bound to the polymer matrix, and grafting the polymer matrix to the halobutyl elastomer by nucleophilic substitution of allyl halide sites, wherein the halobutyl elastomer comprises repeating units derived from at least one C4 to C7 isoolefin monomer and at least one C4 to C14 multiolefin monomer, the halobutyl elastomer having allyl halide sites. CN 201210332453.5A process for preparing a butyl rubber solution, comprising the following steps: dehydrating the butyl rubber micelle water mixture through a vibrating screen; dissolving the dehydrated colloidal particle water mixture obtained above in alkane and/or cycloalkane as solvent to obtain aqueous colloidal solution; performing primary dehydration on the obtained aqueous glue solution through gravity settling dehydration to obtain aqueous glue solution; and carrying out secondary dehydration on the aqueous glue solution obtained in the previous step through electric dehydration to obtain a butyl rubber solution with the water content of less than 0.3 weight percent based on the total weight of the butyl rubber solution.
CN201310521634.7 discloses a method for preparing collagen microfiber based on imidazole type ionic liquid/dimethyl sulfoxide system. The method comprises the steps of taking animal leather as a raw material, taking an imidazole type ionic liquid/dimethyl sulfoxide mixture as a treating agent, treating at 90-130 ℃ to obtain a suspension, centrifuging at a high speed to obtain a precipitate, cleaning the obtained precipitate, and freeze-drying to obtain the collagen microfiber. CN201210196327.1 a process for the preparation of 2- (((1H-benzo [ d ] imidazol-2-yl) methyl) (1-benzyl-1H-benzo [ d ] imidazol-2-yl) amino) acetic acid, more specifically, 2- (((1H-benzo [ d ] imidazol-2-yl) methyl) (1-benzyl-1H-benzo [ d ] imidazol-2-yl) amino) acetic acid and intermediate compounds involved in the synthesis. The method for preparing the novel bisbenzimidazole amino acid compound 2- (((1H-benzo [ d ] imidazole-2-yl) methyl) (1-benzyl-1H-benzo [ d ] imidazole-2-yl) amino) acetic acid (VII) with potential bioactivity provides a thought for synthesis of similar compounds, and also provides a raw material for subsequent pharmacological research of the similar compounds. CN201310533308.8 chiral pyrrolidine functionalized imidazole salt, and a preparation method and application thereof. The chiral pyrrolidine functionalized imidazole salt is brominated 1- [2- (S) - (pyrrolidinyl) methyl ] -3-phenacyl imidazole hydrobromide. The preparation method comprises the following steps: taking natural amino acid L-proline as a starting material, and carrying out multiple steps of conventional organic synthesis reactions such as Boc acylation, carboxylic acid reduction, hydroxyl sulfonylation, nucleophilic substitution of imidazole negative ions, quaternary ammonium salinization of halogenated hydrocarbon, Boc protection removal and the like to prepare the chiral pyrrolidine functionalized imidazole salt. CN201310253407.0 emulsion resin for high throwing power cathode electrophoretic paint and a preparation method thereof, the emulsion resin is composed of three components: the modified epoxy resin accounts for 50-70% of the solid weight of the emulsion resin; the isocyanate at the closed end accounts for 20-40% of the solid weight of the emulsion resin; and (2) adding the modified epoxy resin, the closed-end isocyanate, the imidazolium salt compound and the solvent in sequence, heating to 60 ℃, uniformly stirring, keeping the temperature for 30 minutes, adding the organic acid for neutralization, stirring for 1 hour at 60 ℃, slowly adding deionized water under the stirring state, and continuously stirring for 30 minutes after the addition to obtain the resin emulsion, wherein the imidazolium salt compound accounts for 10-20% of the solid weight of the emulsion resin.
EP2285851(B1), JP5409774(B2) relate to block copolymers and polymer units having the formula A-B formed from a polymer which is an olefin unit of from α to 6 to 22 carbon atoms, B being essentially formed from isobutylene units, to a process for their preparation, to lubricating oil compositions for use therewith and to lubricant compositions comprising such block copolymers. JP2000319461(A) gives a resin composition product having excellent impact resistance, which comprises a transparent polypropylene resin and an isobutylene polymer, a copolymer containing ethylene and an alpha-olefin. KR20010049193(a) provides a vinyl-containing polymer and a process for its preparation, which can be used as a replacement for alpha polyisobutylenes and poly-olefins and can be used in the production of lubricating oils.
The slurry process described by Ullmanns Encyclopedia of Industrial Chemistry (volume A, page 23, 1993) which comprises cationically copolymerizing isobutylene and isoprene in methylene chloride as a solvent and aluminum trichloride as an initiator with the addition of a small amount of water or hydrogen chloride, requires a polymerization temperature of-100 ℃. The solvent method butyl rubber reported in foreign documents is a product obtained by cationic copolymerization of isobutene and isoprene under the catalysis of chloroethane and isopentane as solvent systems and dichloroethylaluminum as catalytic systems. CN1253141A of the company bayer proposes a process for the preparation of butyl rubber polymers having a molecular weight of at least 40 ten thousand by first contacting C4-C14 multiolefin monomers at a temperature in the range of about-100 ℃ to +50 ℃ in the presence of an aliphatic diluent and a catalyst mixture comprising a major amount of a dialkylaluminum halide, with the disadvantage of having limitations in the control of the polymerization reaction. Canadian patent 1019095 uses an alkylaluminum halide, such as ethyl sesquichloride, a co-catalyst of water or hydrogen sulfide, and the solvent isopentane. WO0185810, cn01143371.x, reports an improved process for the preparation of butyl rubber using alkylaluminum halides and aluminum alkoxides, the aluminum alkoxides being co-initiators, and aliphatic hydrocarbons being solvents. RU2071481 reports an initiation system for the preparation of butyl rubber using a solution process with alkylaluminum halides and water, and monoethanolamine, diethanolamine, triethanolamine as a third component, with the amount of ethanolamine being 25-75% of the amount of copolymerization catalyst, contributing to the increase of monomer conversion and reaction temperature.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer of isobutene, isoprene and alkylstyrene, and the prepared polymer has excellent processability and damping performance.
The preparation method of the polymer of isobutene, isoprene and alkylstyrene comprises the following steps: (1) firstly, dissolving an alkylstyrene monomer in ionic liquid; (2) replacing nitrogen for three times in a polymerization kettle under normal pressure, cooling to-50 to-100 ℃, adding methyl chloride as a solvent, adding isobutene, isoprene and the alkyl styrene solution obtained in the step (1), stirring for 10-30 min, adding aniline, adding an initiator for 3-5 times, reacting for 30min to 3h, adding a terminator to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product.
The alkyl styrene is one of o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, o-propyl styrene, m-propyl styrene, p-propyl styrene or styrene with a side chain of C4-C10, preferably o-methyl styrene; the dosage is 10-20 g.
The ionic liquid is imidazole salt, such as one or a mixture of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and the using amount of the ionic liquid is 10-20 g.
The dosage of the isobutene is 200-400 g.
The dosage of the isoprene is 1-2 g.
The polymerization temperature in the invention is preferably-70 to-100 ℃.
The methyl chloride is methyl chloride or methylene chloride; the dosage is 500-1000 g.
The dosage of the aniline is 1-2 g.
The initiator is an initiation system containing a main initiator and a co-initiator.
The preparation method of the initiation system comprises the following steps: adding a main initiator into a flask at-20 to-80 ℃ in an anhydrous and oxygen-free glove box, then adding an auxiliary initiator, wherein the mass ratio of the auxiliary initiator to the main initiator is 8-2: 1, and shaking up and aging for 8-20 min.
The main initiator is one of tert-butyl chloride (t-BuCl), HCL gas and dicumyl chloride (DCC), and the using amount of the main initiator is 1-5 g.
The coinitiator is a complex of an alkylaluminum compound and ether, wherein the alkylaluminum compound is tert-butyl aluminum chloride, isobutyl aluminum dichloride, ethyl aluminum dichloride, triethyl aluminum trichloride and the like, and isobutyl aluminum dichloride is preferred; the ether is aliphatic ether, cyclic ether, crown ether and the like, such as methyl ether, methyl ethyl ether, tetrahydrofuran, benzo-15-crown ether-5, 4' -aminobenzo-18-crown ether-6 and the like, preferably the crown ether, and the complexing mass ratio of the alkyl aluminum compound to the ether is 1: 1 to 3.
The preparation method of the coinitiator comprises the following steps: adding 0.5-30 g of ether and 0.5-20 g of alkyl aluminide into a flask in an anhydrous and oxygen-free glove box at the temperature of-20 to-80 ℃, shaking up, and complexing for 3-8 min.
The terminator is methanol, and the using amount of the terminator is 1-3 g.
The polymer obtained by the invention has the following performance indexes: the molecular weight of the polymer reaches 50,000-150,000, the molecular weight distribution is 2.0-4.0, the mol percentage content of the alkyl styrene in the copolymer is more than 3%, the tensile strength of vulcanized rubber is more than or equal to 13MPa, the glass transition temperature is less than or equal to minus 50 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperatureDegree range of DEG C |
| tgδ≥0.2 | -45℃～-5℃ |
| tgδ≥0.3 | -43℃～-8℃ |
| tgδ≥0.5 | -40℃～-10℃ |
The invention has the beneficial effects that: (1) compared with the prior solution method for preparing the butyl rubber, the third component of the alkyl styrene is added, the copolymerization of the isobutene and the isoprene is linear high molecular polymer, and the addition of the alkyl styrene increases the rigid structure of the molecule, so that the polymer has good flexibility and good rigidity; (2) the addition of the alkylstyrene enables the processability of the rubber to be better, and the rubber is firstly dissolved into the ionic liquid and is easier to add in polymerization; aniline is a nucleophilic functional group, the molecular weight distribution of the polymer is narrower due to the addition of aniline, the processing performance is more stable, and the mechanical property of the polymer is improved due to the addition of aniline containing a rigid structure; (3) the initiator is added for several times, and the reaction is stable and controllable; the polymer obtained by the invention is a brand new material, and has better damping performance.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any modifications made on the basis of the present invention do not depart from the spirit of the present invention.
The required medicines are all commercial industrial products;
the molecular weight of the polymer is determined by adopting a Gel Permeation Chromatography (GPC) method, the molar content of the alkyl styrene in the polymer is determined by adopting a nuclear magnetic resonance spectroscopy method, the tensile strength is tested according to the national standard GB/T528-1998, the glass transition temperature is tested according to the GB/T528-2009 standard, the dynamic mechanical property is tested by a viscoelastic spectrometer (DMA), and the test standard is GJB 981-.
Example 1
(1) Firstly, 10g of o-methylstyrene monomer is dissolved in 10g of ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 2g of crown ether into a flask in an anhydrous and oxygen-free glove box at the temperature of-20 ℃, adding 2g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 5 min; 1g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 10 min; (3) and (2) replacing the polymerization kettle with nitrogen for three times under normal pressure, cooling to-50 ℃, adding 500g of chloromethane as a solvent, adding 200g of isobutene, 1g of isoprene and the o-methylstyrene solution obtained in the step (1), adding 1g of aniline, adding the initiator obtained in the step (2) for 3 times, reacting for 30min, adding 3g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 60,000, the molecular weight distribution is 2.5, the mol percentage content of o-methylstyrene in the copolymer is 3.5 percent, the tensile strength of vulcanized rubber is 13.5MPa, the glass transition temperature is-70 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -43℃～-9℃ |
| tgδ≥0.3 | -40℃～-10℃ |
| tgδ≥0.5 | -38℃～-11℃ |
Comparative example 1
The experimental conditions were the same as in example 1, except that 10g of o-methylstyrene was not added, and the results were: the molecular weight of the polymer is 30,000, the molecular weight distribution is 3.5, the tensile strength of vulcanized rubber is 9MPa, the glass transition temperature is-45 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -30℃～-2℃ |
| tgδ≥0.3 | -28℃～-5℃ |
| tgδ≥0.5 | -35℃～-8℃ |
Example 2
(1) Firstly, 10g of m-methylstyrene monomer is dissolved in 10g of ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 10g of crown ether into a flask in an anhydrous and oxygen-free glove box at-40 ℃, adding 5g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 8 min; 5g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 20 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-50 ℃, adding 1000g of chloromethane as a solvent, adding 400g of isobutene, 2g of isoprene and the m-methylstyrene solution obtained in the step (1), adding 2g of aniline, adding the initiator obtained in the step (2) for 4 times, reacting for 3 hours, adding 3g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 80,000, the molecular weight distribution is 2.3, the mol percentage content of the intermediate methylstyrene in the copolymer is 3.2 percent, the tensile strength of the vulcanized rubber is 15MPa, the glass transition temperature is-70 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -45℃～-5℃ |
| tgδ≥0.3 | -43℃～-9℃ |
| tgδ≥0.5 | -40℃～-10℃ |
Comparative example 2
The experimental conditions were the same as in example 2, except that 10g of m-methylstyrene was not added, and the results were: the molecular weight of the polymer is 50,000, the molecular weight distribution is 3.2, the tensile strength of vulcanized rubber is 10MPa, the glass transition temperature is-40 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -35℃～-5℃ |
| tgδ≥0.3 | -33℃～-9℃ |
| tgδ≥0.5 | -30℃～-10℃ |
Example 3
(1) Firstly, 20g of p-methylstyrene monomer is dissolved in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 7.5g of crown ether into a flask in an anhydrous and oxygen-free glove box at the temperature of-60 ℃, adding 2.5g of isobutylaluminum dichloride and complexing with the crown ether, shaking up and complexing for 4 min; 5g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 8 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-100 ℃, adding 1000g of chloromethane as a solvent, adding 400g of isobutene, 1g of isoprene and the p-methylstyrene solution obtained in the step (1), adding 2g of aniline, adding the initiator obtained in the step (2) for 5 times, reacting for 2 hours, adding 2g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 150,000, the molecular weight distribution is 2.2, the mol percentage content of p-methylstyrene in the copolymer is 3.1 percent, the tensile strength of vulcanized rubber is 16.3MPa, the glass transition temperature is-69 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -45℃～-5℃ |
| tgδ≥0.3 | -43℃～-8℃ |
| tgδ≥0.5 | -39℃～-10℃ |
Comparative example 3
The experimental conditions were the same as in example 3 except that 20g of p-methylstyrene was not added, and the results were: the polymer had a molecular weight of 90,000 and a molecular weight distribution of 3.9. The vulcanized rubber has the tensile strength of 10MPa, the glass transition temperature of-50 ℃ and the damping performance of:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -27℃～0℃ |
| tgδ≥0.3 | -25℃～-5℃ |
| tgδ≥0.5 | -20℃～-10℃ |
Example 4
(1) Firstly, 10g of o-methylstyrene monomer is dissolved in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 6g of crown ether into a flask in an anhydrous and oxygen-free glove box at the temperature of-80 ℃, adding 2g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 8 min; 1g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 8 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-100 ℃, adding 1000g of chloromethane as a solvent, adding 200g of isobutene, 1g of isoprene and the o-methylstyrene solution obtained in the step (1), adding 2g of aniline, adding the initiator obtained in the step (2) for 3 times, reacting for 1 hour, adding 3g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 150,000, the molecular weight distribution is 2.3, the mol percentage content of o-methylstyrene in the copolymer is 3.5 percent, the tensile strength of vulcanized rubber is 15.8MPa, the glass transition temperature is-73 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -43℃～-5℃ |
| tgδ≥0.3 | -40℃～-9℃ |
| tgδ≥0.5 | -39℃～-10℃ |
Comparative example 4
The experimental conditions were the same as in example 4 except that 10g of o-methylstyrene was not added, and the results were: the molecular weight of the polymer is 90,000, the molecular weight distribution is 4.5, the tensile strength of vulcanized rubber is 8MPa, the glass transition temperature is-46 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -25℃～5℃ |
| tgδ≥0.3 | -23℃～2℃ |
| tgδ≥0.5 | -20℃～-0℃ |
Example 5
(1) Firstly, 20g of m-methylstyrene monomer is dissolved in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 3.75g of crown ether into a flask in an anhydrous and oxygen-free glove box at the temperature of-30 ℃, adding 1.25g of isobutylaluminum dichloride and the crown ether for complexing, shaking up and complexing for 6 min; 1g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 15 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-70 ℃, adding 500g of chloromethane as a solvent, adding 400g of isobutene, 2g of isoprene and the m-methylstyrene solution obtained in the step (1), adding 1g of aniline, adding the initiator obtained in the step (2) for 4 times, reacting for 2 hours, adding 2g of methanol to terminate the reaction, and carrying out flash evaporation, filtration and drying on the terminated solution to obtain a finished product. The molecular weight of the polymer is 100,000, the molecular weight distribution is 2.3, the mol percentage content of the intermediate methylstyrene in the copolymer is 3.4 percent, the tensile strength of the vulcanized rubber is 16.1MPa, the glass transition temperature is-65 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -44℃～-5℃ |
| tgδ≥0.3 | -43℃～-8℃ |
| tgδ≥0.5 | -39℃～-10℃ |
Comparative example 5
The experimental conditions were the same as in example 5, except that 1g of aniline was not added, and the results were: the molecular weight of the polymer is 90,000, the molecular weight distribution is 3.8, the tensile strength of vulcanized rubber is 10.3MPa, the glass transition temperature is-50 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -25℃～-5℃ |
| tgδ≥0.3 | -23℃～-8℃ |
| tgδ≥0.5 | -20℃～-10℃ |
Example 6
(1) Firstly, 20g of p-methylstyrene monomer is dissolved in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 15g of crown ether into a flask in an anhydrous and oxygen-free glove box at the temperature of-50 ℃, adding 15g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 8 min; 5g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the ether into the main initiator, shaking up and aging for 20 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-90 ℃, adding 1000g of chloromethane as a solvent, adding 400g of isobutene, 2g of isoprene and the p-methylstyrene solution obtained in the step (1), adding 2g of aniline, adding the initiator obtained in the step (2) for 5 times, reacting for 1 hour, adding 3g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 140,000, the molecular weight distribution is 2.2, the mol percentage content of p-methylstyrene in the copolymer is 3.3%, the tensile strength of vulcanized rubber is 14.8MPa, the glass transition temperature is-75 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -45℃～-8℃ |
| tgδ≥0.3 | -43℃～-10℃ |
| tgδ≥0.5 | -40℃～-12℃ |
Comparative example 6
The experimental conditions were the same as in example 6, except that 2g of aniline was not added, and the results were: the molecular weight of the polymer is 130,000, the molecular weight distribution is 4.9, the tensile strength of vulcanized rubber is 10.3MPa, the glass transition temperature is-55 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -27℃～-5℃ |
| tgδ≥0.3 | -25℃～-7℃ |
| tgδ≥0.5 | -24℃～-10℃ |
Example 7
(1) Firstly, dissolving 15g of o-methylstyrene monomer in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 15g of crown ether into a flask in an anhydrous and oxygen-free glove box at-70 ℃, adding 5g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 5 min; 5g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 10 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-100 ℃, adding 500g of chloromethane as a solvent, adding 300g of isobutene, 1.5g of isoprene and the o-methylstyrene solution obtained in the step (1), adding 2g of aniline, adding the initiator obtained in the step (2) for 3 times, reacting for 3 hours, adding 2g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 150,000, the molecular weight distribution is 2.0, the mol percentage content of o-methylstyrene in the copolymer is 3.3 percent, the tensile strength of vulcanized rubber is 16.8MPa, the glass transition temperature is-72 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -45℃～-6℃ |
| tgδ≥0.3 | -43℃～-8℃ |
| tgδ≥0.5 | -40℃～-11℃ |
Comparative example 7
The experimental conditions were the same as in example 7, except that 2g of aniline was not added, and the results were: the molecular weight of the polymer is 130,000, the molecular weight distribution is 4.6, the tensile strength of vulcanized rubber is 10.6MPa, the glass transition temperature is-48 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -30℃～-5℃ |
| tgδ≥0.3 | -28℃～-7℃ |
| tgδ≥0.5 | -25℃～-10℃ |
Example 8
(1) Firstly, dissolving 15g of m-methylstyrene monomer in 10g of ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide; (2) preparing an initiator complex: adding 14g of crown ether into a flask in an anhydrous and oxygen-free glove box at-60 ℃, adding 7g of isobutylaluminum dichloride to be complexed with the crown ether, and shaking up for complexing for 8 min; 3g of the primary initiator tert-butyl chloride (t-BuCl) was added to another flask; then adding the isobutyl aluminum dichloride auxiliary initiator complexed with the crown ether into the main initiator, shaking up and aging for 10 min; (3) replacing a polymerization kettle with nitrogen for three times under normal pressure, cooling to-50 ℃, adding 500g of chloromethane as a solvent, adding 400g of isobutene, 1.5g of isoprene and the m-methylstyrene solution obtained in the step (1), adding 1g of aniline, adding the initiator obtained in the step (2) for 3 times, reacting for 3 hours, adding 1g of methanol to terminate the reaction, and flashing, filtering and drying the terminated solution to obtain a finished product. The molecular weight of the polymer is 60,000, the molecular weight distribution is 2.5, the mol percentage content of the intermediate methylstyrene in the copolymer is 3.2 percent, the tensile strength of the vulcanized rubber is 16.4MPa, the glass transition temperature is-69 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -45℃～-5℃ |
| tgδ≥0.3 | -43℃～-8℃ |
| tgδ≥0.5 | -40℃～-10℃ |
Comparative example 8
The experimental conditions were the same as in example 8, except that 1g of aniline was not added, and the results were: the molecular weight of the polymer is 50,000, the molecular weight distribution is 3.8, the tensile strength of vulcanized rubber is 12.3MPa, the glass transition temperature is-52 ℃, and the damping performance is as follows:
| tg delta value range | Damping temperature range deg.C |
| tgδ≥0.2 | -33℃～-5℃ |
| tgδ≥0.3 | -30℃～-8℃ |
| tgδ≥0.5 | -28℃～-10℃ |
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (14)
1. A method for preparing a polymer of isobutylene, isoprene and alkylstyrene, comprising the steps of: (1) firstly, dissolving an alkylstyrene monomer in ionic liquid; (2) replacing the polymerization kettle with nitrogen for three times under normal pressure, cooling to-50-100 ℃, adding methyl chloride as a solvent, adding isobutene, isoprene and the alkylstyrene ionic liquid solution obtained in the step (1), stirring for 10-30 min, adding aniline, adding an initiator for 3-5 times, carrying out polymerization for 30 min-3 h, adding a terminator to terminate the reaction, and carrying out flash evaporation, filtration and drying on the terminated solution to obtain a finished product; the ionic liquid is an imidazolium salt; the initiator is an initiation system containing a main initiator and an auxiliary initiator; the main initiator is selected from one of tert-butyl chloride, HCl gas and dicumyl chloride; the co-initiator is a complex of one of tert-butyl aluminum chloride, isobutyl aluminum dichloride, ethyl aluminum dichloride and triethyl aluminum trichloride and ether, and the complexing mass ratio of one of tert-butyl aluminum chloride, isobutyl aluminum dichloride, ethyl aluminum dichloride and triethyl aluminum trichloride to ether is 1: 1-3; the mass ratio of the auxiliary initiator to the main initiator in the initiation system is 8-2: 1.
2. The method according to claim 1, wherein the alkylstyrene is one of o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-propylstyrene, m-propylstyrene and p-propylstyrene, and the amount of the alkylstyrene is 10 to 20 g.
3. The method according to claim 1, wherein the ionic liquid is one or more of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and the dosage is 10-20 g.
4. The method according to claim 1, wherein the amount of isobutylene is 200 to 400 g.
5. The method according to claim 1, wherein the amount of isoprene used is 1 to 2 g.
6. The process according to claim 1, wherein the polymerization temperature is from-70 to-100 ℃.
7. The method according to claim 1, wherein the methyl chloride is methyl chloride or methylene chloride and is used in an amount of 500 to 1000 g.
8. The method according to claim 1, wherein the aniline is used in an amount of 1 to 2 g.
9. The method according to claim 1, wherein the terminator is methanol in an amount of 1 to 3 g.
10. The method of claim 1, wherein the initiation system is prepared by: and (3) adding a main initiator and an auxiliary initiator into a flask in an anhydrous and oxygen-free glove box at the temperature of-20 to-80 ℃, shaking uniformly and aging for 8-20 min.
11. The method according to claim 1, wherein the amount of the primary initiator is 1 to 5 g.
12. The method of claim 1, wherein the coinitiator is prepared by: adding 0.5-30 g of ether, 0.5-20 g of tert-butyl aluminum chloride, isobutyl aluminum dichloride, ethyl aluminum dichloride and trichlorotriethyl aluminum into a flask in an anhydrous and oxygen-free glove box at the temperature of-20 to-80 ℃, shaking up, and complexing for 3-8 min.
13. The method according to claim 12, wherein the ether is one of methyl ether, methyl ethyl ether, tetrahydrofuran, benzo-15-crown-5, 4' -aminobenzo-18-crown-6.
14. The method of claim 12, wherein the ether is a crown ether.
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