CN106046228B - Method for preparing poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer - Google Patents
Method for preparing poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer Download PDFInfo
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Abstract
The invention discloses a method for preparing a poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer, which comprises the following steps of ageing and complexing a main initiator and a co-initiator into an initiation system, taking isobutylene, alkylstyrene and isoprene as raw materials, adding one of esters, amides and ketones as a third component, and preparing the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer by cationic polymerization in a solvent of methyl chloride and/or hexane.
Description
Technical Field
The invention belongs to the technical field of elastomer synthesis, and particularly relates to a method for modifying butyl rubber, in particular to a method for preparing a poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer.
Background
Butyl rubber (IIR) is an elastomer obtained by cationic polymerization of isobutene and a small amount of isoprene, has high saturation, excellent air tightness, low glass transition temperature, excellent damping property and aging resistance, and is widely applied to the fields of automobile inner tubes, air-tight layer materials, medical bottle stoppers and the like. However, the traditional butyl rubber has many defects, the compatibility of the butyl rubber with other rubbers is poor, the butyl rubber is not beneficial to blending and mixing with other rubbers, and molecular chains contain unsaturated double bonds, so that the butyl rubber is easy to crosslink in the later processing process of the rubber and generates scorching. The poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer synthesized by taking p-methylstyrene (p-tert-butylstyrene) as a third monomer has the isobutylene structural unit content of more than 90 percent, has air tightness and damping performance similar to those of butyl rubber, has thermal-oxidative aging resistance and ozone resistance similar to those of ethylene propylene rubber, and has more excellent performance than that of the traditional butyl rubber. Meanwhile, the addition of the alkyl styrene enhances the adhesive force of the rubber to the carbon black and increases the modulus of the rubber. The poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer has good air tightness, impact resilience, thermal stability, ozone resistance, fatigue resistance and wear resistance, so that the poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer can almost completely replace rubber materials such as tire sidewalls, treads, tire bodies and the like. The copolymer has wide application range, can be used in automobile tires, improves the dynamic performance of the tires, reduces the rolling resistance and improves the wet skid resistance, and can also be used in the aspects of damping materials, tire air barriers, conveying belts, rubber hoses and the like.
U.S. patents U.S. Pat. Nos. 5,126,8A and U.S. Pat. No. 5,8, 5A describe in detail the synthesis of poly (isobutylene-co-p-methylstyrene) copolymers at-80 to-100 ℃ using aluminum trichloride and an aluminum alkyl as the initiating system. In the literature, the initiator is added into a reaction system in a direct adding mode without aging, the activity of the initiation system is difficult to control, and the initiator only selects aluminum trichloride and ethyl aluminum dichloride. U.S. patents U.S.5430118a and U.S. patent u.s.5162445a describe the synthesis of polymers by the solution method, using solvents in which the volume ratio of methyl chloride to hexane is 6/4. The glue solution has high viscosity, poor reaction heat transfer, serious wall-hanging phenomenon of the glue solution and short synthesis production period. And the polymerization reaction temperature is lower, the energy consumption is higher, and the molecular weight distribution is more than 2. Chinese patent CN103694391A describes a method for preparing isobutylene-p-methylstyrene-isoprene copolymer by catalytic polymerization of a catalyst mixture formed by aluminum trichloride and isoprene, and ethanol is used as a terminator, wherein the initiation system adopted is as follows: alkyl aluminium chlorideOne of (including ethyl aluminum dichloride, triethyl aluminum trichloride) and titanium tetrachloride is taken as a coinitiator; taking one of water, HCl gas, dicumyl chloride (DCC) and 2-chloro-2, 4, 4-Trimethylpentane (TMPCL) as a main initiator, aging for 0-30min, and adding into the reaction system for polymerization, wherein the terminator is methanol. No such addition of a third component to reduce the rate of polymerization is involved in any of the above polymerization systems. US5162445 discloses elastomeric copolymers of isobutylene and para-methylstyrene, using free radical halogenation. The copolymer contains about 0.5 to 20 wt% of p-methylstyrene, preferably bromine atoms, halogenated such that up to about 65% of the methyl substituents present on the benzene ring contain bromine atoms. H is added during bromination2O2For improving the halogenation efficiency, this process has been disclosed in US3018275 and GB 867737. Chinese patent CN1225648A describes the addition of azobisisobutyronitrile, azobisisoheptonitrile, azobis (2-methylbutyronitrile) nitrile as radical initiator under light conditions, with bromine as halogenating agent and H as oxidant2O2In the form of an emulsion, the halogenation site is a copolymer of a C4 to C7 isomonoolefin and a para-alkylstyrene. The halogenation system adopts azodiisoheptonitrile as a free radical initiator and an oxidant H under the conditions of water bath heating at 20-60 ℃ and illumination2O2The liquid was added directly and after the reaction was complete the reaction was stopped by adding NaOH solution. The halogenated object is a poly (isobutylene-co-p-methylstyrene-co-isoprene) random copolymer. The above patents relate to the halogenated modification of poly (isobutylene-co-p-methylstyrene-co-isoprene) random copolymers. In synthesis and characterization of isobutylene-p-methylstyrene random copolymer published by Guowenli research team, isobutylene and p-methylstyrene are used as monomers to synthesize poly (isobutylene-co-p-methylstyrene), and isoprene is not added in the document.
Disclosure of Invention
It is an object of the present invention to overcome the deficiencies of the prior art and to provide a process for preparing a poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer.
The purpose of the invention is realized by the following technical scheme.
A method of preparing a poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer comprising the steps of: the main initiator and the coinitiator are aged and compounded into an initiating system, isobutene, alkyl styrene and isoprene are used as raw materials, one of esters, amides and ketones is added to serve as a third component, and the poly (isobutene-co-alkyl styrene-co-isoprene) random copolymer is prepared through cationic polymerization in a solvent of methyl chloride and/or hexane.
Further, the main initiator is one of water, HCl gas, dicumyl chloride (DCC) and 2-chloro-2, 4, 4-Trimethylpentane (TMPCL); the coinitiator is one of alkyl aluminum chloride and titanium tetrachloride; the alkyl aluminum chloride comprises ethyl aluminum dichloride and triethyl aluminum trichloride; the aging time of the main initiator and the co-initiator is 1-30 min.
Further, the alkylstyrene is one of p-methylstyrene, p-ethylstyrene, m-methylstyrene, o-methylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, p-propylstyrene and isopropylstyrene, and preferably p-methylstyrene or p-tert-butylstyrene.
Further, the esters are selected from methyl acetate (MtOAc), ethyl acetate (EtOAc), tert-butyl acetate (t-BuOAc), preferably ethyl acetate (EtOAc); the amide is selected from N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), Triethylamine (TEA), preferably N, N-Dimethylformamide (DMF); the ketones are selected from acetone, butanone, pentanone, propiophenone, preferably acetone.
Further, one of the esters, amides and ketones is taken as a third component, and is added into the reactor along with a polymerization monomer when the monomer is fed, or is added into the reactor along with an initiator system after being aged together with the initiator system; the concentration of the esters, amides and ketones as the third component is 1 × 10-3～1×10-5mol/L, ratio to main initiator concentration: 0.1 to 10. The esters, amides and ketones as the third component of cationic polymerization can increase the molecular weight of the polymer, reduce the molecular weight distribution index, reduce the polymerization rate and reduceExothermic amount, increase polymerization temperature.
Further, the concentration of the isobutene raw material is 10-35 wt%.
Further, the polymerization temperature is from-90 ℃ to-40 ℃, the number average molecular weight of the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer is from 50,000 g/mol to 700,000g/mol, and the molecular weight distribution is from 1.2 to 3.0.
Further, in the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer, the amount of alkylstyrene structural units accounts for 1 to 5% of the amount of isobutylene structural units, and the amount of isoprene structural units accounts for 1 to 5% of the amount of isobutylene structural units; the conversion of isobutylene, alkylstyrene and isoprene monomers is 50-100%.
The invention adopts an initiating system of a main initiator and a co-initiator, and the initiating system is added into a polymerization system after aging to obtain the poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer with better molecular weight and molecular weight distribution. The method improves the halogenation efficiency of the poly (isobutylene-co-p-methylstyrene-co-isoprene) copolymer by adding isoprene, and is beneficial to the implementation of a post vulcanization process. Meanwhile, the invention takes esters, amides and ketones as a third component of the positive ion copolymerization to stabilize the positive ion active center, control the reaction speed, improve the molecular weight of the polymer and reduce the molecular weight distribution, and provides a method for synthesizing the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer at higher temperature. The rubber is beneficial to increasing the vulcanization rate, enhancing the adhesion of the rubber to carbon black, and improving the vulcanization performance, the subsequent processing performance and the compatibility with other rubbers. The poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer prepared by the method can be used for tire inner tubes, tubeless tire airtight layers, medical bottle stoppers, shock absorption materials and damping materials.
Drawings
FIG. 1 is a graph showing the relationship between the temperature of the reaction vessel and the third monomer in the reaction process of the present invention.
FIG. 2 is a graph showing the relationship between the molecular weight of the copolymer of examples 1 to 3 of the present invention and the third component.
Wherein, the square scatter plot in FIG. 1 is a curve of the temperature of the reaction kettle changing with time without adding the third component; the triangular scatter plot is a plot of the temperature of the reaction vessel as a function of time with the addition of 0.55mmol/L Ethyl Acetate (EAC) as the third component.
In FIG. 2, the third component was not added in example 1, 15ml of ethyl acetate (0.1M) was added in example 2, and 10ml of N, N-dimethylformamide (0.1M) was added in example 3. The earlier the peak time is, the larger the molecular weight is, so that it can be seen from the graph that the molecular weight is increased and the molecular weight distribution index becomes smaller by adding the third component.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
A method for preparing poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer includes the following steps of aging and complexing a main initiator and a co-initiator into an initiation system, taking isobutylene, alkylstyrene and isoprene as raw materials, adding one of esters, amides and ketones as a third component, and preparing the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer in a solvent of methyl chloride and/or hexane through cationic polymerization.
Wherein the main initiator is one of water, HCl gas, dicumyl chloride (DCC) and 2-chloro-2, 4, 4-Trimethylpentane (TMPCL); the coinitiator is one of alkyl aluminum chloride and titanium tetrachloride; the alkyl aluminum chloride comprises ethyl aluminum dichloride and triethyl aluminum trichloride; the aging time of the main initiator and the co-initiator is 1-30 min.
Wherein the alkylstyrene is one of p-methylstyrene, p-ethylstyrene, m-methylstyrene, o-methylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, p-propylstyrene and isopropylstyrene. P-methylstyrene or p-tert-butylstyrene are preferred.
Wherein the esters are selected from methyl acetate (MtOAc), ethyl acetate (EtOAc), tert-butyl acetate (t-BuOAc), preferably ethyl acetate (EtOAc); the amide is selected from N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), Triethylamine (TEA), preferably N, N-Dimethylformamide (DMF); the ketones are selected from acetone, butanone, pentanone, propiophenone, preferably acetone.
Wherein, one of the esters, amides and ketones is taken as a third component, and is added into the reactor along with the polymerization monomer when the monomer is fed, or is added into the reactor along with the initiator system after being aged together with the initiator system; the concentration of the esters, amides and ketones as the third component is 1 × 10-3～1×10-5mol/L, ratio to main initiator concentration: 0.1 to 10. The esters, amides and ketones as the third component of the cationic polymerization can increase the molecular weight of the polymer, reduce the molecular weight distribution index, reduce the polymerization rate, reduce the heat release and improve the polymerization temperature.
Wherein the concentration of the isobutene raw material is 10-35 wt%.
Wherein the polymerization temperature is-90 ℃ to-40 ℃, the number average molecular weight of the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer is 50,000-700,000g/mol, and the molecular weight distribution is 1.2 to 3.0.
Wherein, in the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer, the monomer conversion rate of isobutylene, alkylstyrene and isoprene is 50-100%.
Wherein the isobutylene monomer concentration is 10 wt% to 35 wt%, and in the poly (isobutylene-co-alkylstyrene) random copolymer, the amount of alkylstyrene structural units accounts for 1 to 5% of the amount of isobutylene structural units, and the amount of isoprene structural units accounts for 1 to 5% of the amount of isobutylene structural units.
The first implementation mode comprises the following steps: when monomer is fed, the third component is added into the reactor along with the monomer material
(1) Feeding into a reaction kettle: at the temperature of between 90 ℃ below zero and 40 ℃ below zero, adding a hexane and/or methyl chloride solvent into a reaction kettle in proportion, adding isobutene, alkyl styrene and isoprene, and one of third components of esters, amides and ketones, and uniformly mixing.
(2) Initiator system configuration: the co-initiator and the main initiator are mixed well and diluted with hexane and aged at low temperature for 1-30 min.
(3) Polymer synthesis: adding an initiator system into a reaction kettle at the temperature of between 90 ℃ below zero and 40 ℃ below zero, releasing a large amount of heat in the process of synthesizing the copolymer, and adding a terminator methanol to terminate the polymerization reaction when the temperature in the reaction kettle rises to a certain value. And raising the temperature of the reaction kettle again, and removing the solvent to obtain the solid poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer.
The second method comprises the following steps: mixing the third component with the initiating system, aging together, and adding into the reactor with the initiating system
(1) Feeding into a reaction kettle: at the temperature of-90 to-40 ℃, adding a solvent of hexane and/or chloromethane into a reaction kettle in proportion, adding isobutene, alkyl styrene and isoprene, and uniformly mixing;
(2) initiator system configuration: fully mixing the co-initiator and the main initiator, diluting with hexane, adding one of esters, amides and ketones of a third component into an initiation system, and aging at low temperature for 1-30 min;
(3) polymer synthesis: adding an initiator system into a reaction kettle at the temperature of between 90 ℃ below zero and 40 ℃ below zero, releasing a large amount of heat in the process of synthesizing the copolymer, and adding a terminator methanol to terminate the polymerization reaction when the temperature in the reaction kettle rises to a certain value. And raising the temperature of the reaction kettle again, and removing the solvent to obtain the solid poly (isobutylene-co-alkylstyrene-co-isoprene) copolymer.
The present invention will be further illustrated by the following examples which are given by way of illustration of the invention.
Example 1
480g of hexane, 720g of methyl chloride, 300g of isobutene, 3.88g of isoprene and 33.56g of p-methylstyrene are added to a reaction kettle at the temperature of-90 ℃, fully mixed, the concentration of isobutene monomer is 20 wt%, and 5.0ml of trichlorotriethylaluminum (0.4M) and 1.25ml of CH are taken2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for dilution, and aging at low temperature for 5 min. The diluted and aged initiator system is pressed into a reaction kettle by nitrogen to initiate polymerization, and the polymerization temperature is keptThe reaction was stopped by adding 20ml of pre-cooled methanol when the temperature was raised to-40 ℃.
Example 2
480g of hexane, 720g of methyl chloride, 300g of isobutene, 3.88g of isoprene and 33.56g of p-methylstyrene are added to a reaction kettle at the temperature of-90 ℃, fully mixed, the concentration of isobutene monomer is 20 wt%, and 5.0ml of trichlorotriethylaluminum (0.4M) and 1.25ml of CH are taken2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for dilution, adding 15ml of ethyl acetate (0.1M), and aging at low temperature for 5 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 3
480g of hexane, 720g of methyl chloride, 300g of isobutene, 3.88g of isoprene and 33.56g of p-methylstyrene are added into a reaction kettle at the temperature of-90 ℃, fully mixed, the concentration of isobutene monomer is 20 wt%, 7.5ml of ethyl aluminum dichloride (0.3M) and 1.25ml of CH are taken2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for dilution, adding 10ml of N, N-dimethylformamide (0.1M), fully mixing, and aging at low temperature for 5 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 4
480g of hexane, 720g of methyl chloride, 300g of isobutene, 3.88g of isoprene and 33.56g of p-methylstyrene are added into a reaction kettle at the temperature of-90 ℃ and fully mixed, the concentration of isobutene monomer is 20 wt%, 7.5ml of ethyl aluminum dichloride (0.3M) and 20mg of HCl gas are taken and mixed to prepare an initiating system, 40ml of hexane is added for dilution, 20ml of acetone (0.1M) is added for fully mixing, and the mixture is aged for 5min at low temperature. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 5
At the temperature of minus 80 ℃, 600g of hexane, 600g of chloromethane and isobutyl are added into a reaction kettle300g of olefin, 11.63g of isoprene and 20.17g of p-methylstyrene were thoroughly mixed to obtain a 20 wt% isobutylene monomer, and 3.5ml of triethylaluminum trichloride (0.4M) and 1.00ml of CH2Cl2(0.12M) saturated aqueous solution, mixing to obtain initiation system, adding 40ml hexane for dilution, and aging at low temperature for 10 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 6
600g of hexane, 600g of methyl chloride, 300g of isobutene, 11.63g of isoprene and 20.17g of p-methylstyrene are added to a reaction kettle at the temperature of-80 ℃, fully mixed, the isobutene monomer concentration is 20 wt%, and 3.5ml of trichlorotriethylaluminum (0.4M) and 1.00ml of CH are taken2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for dilution, adding 15ml of ethyl acetate (0.1M), and aging at low temperature for 10 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 7
600g of hexane, 600g of methyl chloride, 300g of isobutene, 11.63g of isoprene and 20.17g of p-methylstyrene are added into a reaction kettle at the temperature of-80 ℃ and fully mixed, the concentration of the isobutene monomer is 20 wt%, 4.5ml of ethyl aluminium dichloride (0.3M) and 1.25ml of CH2Cl2(0.12M) saturated aqueous solution are taken and mixed to prepare an initiating system, 40ml of hexane is added for dilution, 10ml of N, N-dimethylformamide (0.1M) is added for fully mixing, and the mixture is aged for 10min at low temperature. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 8
At the temperature of minus 80 ℃, 600g of hexane, 600g of methyl chloride, 300g of isobutene, 11.63g of isoprene and 20.17g of p-methylstyrene are added into a reaction kettle and fully mixed, the concentration of isobutene monomer is 20 wt%, 4.5ml of ethyl aluminum dichloride (0.3M) and 15mg of HCl gas are taken and mixed to prepare an initiating system, 40ml of hexane is added for dilution, 20ml of acetone (0.1M) is added for fully mixing, and the mixture is aged for 10min at low temperature. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 9
720g of hexane, 480g of methyl chloride, 300g of isobutylene, 25.9g of isoprene and 9.11g of p-tert-butylstyrene were added to a reaction vessel at-70 ℃ and mixed thoroughly, the isobutylene monomer concentration was 20 wt%, and 2.5ml of triethylaluminum trichloride (0.4M) and 0.60ml of CH were added2Cl2(0.12M) saturated aqueous solution, mixing to obtain initiation system, adding 40ml hexane for dilution, and aging at low temperature for 20 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 10
720g of hexane, 480g of methyl chloride, 300g of isobutylene, 19.38g of isoprene and 9.11g of p-tert-butylstyrene were added to a reaction vessel at-70 ℃ and mixed thoroughly, the isobutylene monomer concentration was 20 wt%, and 2.5ml of triethylaluminum trichloride (0.4M) and 0.60ml of CH were added2Cl2(0.12M) saturated aqueous solution, mixing to obtain initiation system, adding 40ml hexane for dilution, adding 15ml ethyl acetate (0.1M), and aging at low temperature for 20 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 11
720g of hexane, 480g of methyl chloride, 300g of isobutene, 19.38g of isoprene and 9.11g of p-tert-butylstyrene were added to a reaction kettle at-70 ℃ and mixed thoroughly, the isobutene monomer concentration was 20 wt%, and 3.0ml of ethyl aluminum dichloride (0.3M) and 0.80ml of CH were taken2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for dilution, adding 10ml of N, N-dimethylformamide (0.1M), fully mixing, and aging at low temperature for 20 min. The diluted and aged initiator system is pressed into a reaction kettle by nitrogen to initiate polymerization, 20ml of precooled methanol is added to terminate the reaction when the polymerization temperature rises to minus 40 DEG CShould be used.
Example 12
720g of hexane, 480g of methyl chloride, 300g of isobutene, 19.38g of isoprene and 9.11g of p-tert-butyl styrene are added into a reaction kettle at the temperature of-70 ℃ and are fully mixed, the concentration of isobutene monomer is 20 wt%, 3.0ml of ethyl aluminum dichloride (0.3M) and 12mg of HCl gas are taken and mixed to prepare an initiating system, 40ml of hexane is added for dilution, 20ml of acetone (0.1M) is added for full mixing, and the mixture is aged for 20min at low temperature. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-40 ℃.
Example 13
1200g of methyl chloride, 646g of isobutene, 8.01g of isoprene and 18.83g of p-tert-butyl styrene are added into a reaction kettle at the temperature of-60 ℃, 15ml of ethyl acetate (0.1M) is added and fully mixed, the concentration of an isobutene monomer is 35 wt%, 5.0ml of trichlorotriethylaluminum (0.4M) and 1.2ml of 2-chloro-2, 4, 4-trimethylpentane TMPCl (0.4M) are taken and mixed to prepare an initiating system, 40ml of hexane is added for fully mixing, and the mixture is aged for 1min at low temperature. And (3) pressing the diluted initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-30 ℃.
Example 14
1200g of methyl chloride, 646g of isobutene, 8.01g of isoprene and 18.83g of p-tert-butyl styrene are added into a reaction kettle at the temperature of-60 ℃, 15ml of ethyl acetate (0.1M) is added and fully mixed, the concentration of isobutene monomer is 35 wt%, 7.5ml of ethyl aluminum dichloride (0.3M) and 1ml of DCC (0.5M) are taken and mixed to prepare an initiation system, 40ml of hexane is added for fully mixing and fully mixing, and the mixture is aged for 1min at low temperature. And (3) pressing the diluted initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-30 ℃.
Example 15
1200g of methyl chloride, 646g of isobutene, 8.01g of isoprene and 18.83g of p-tert-butyl styrene are added into a reaction kettle at the temperature of-60 ℃, 10ml of N, N-dimethylformamide (0.1M) is added and fully mixed, the concentration of isobutene monomer is 35 wt%, 2ml of titanium tetrachloride (0.4M) and 15mg of HCl gas are taken and mixed to prepare an initiation system, 40ml of hexane is added for dilution and full mixing, and the mixture is aged for 1min at low temperature. And (3) pressing the diluted initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-30 ℃.
Example 16
1200g of hexane, 646g of isobutene, 43.59g of isoprene and 102.57g of p-tert-butylstyrene are added into a reaction kettle at the temperature of-50 ℃, 10ml of N, N-dimethylformamide (0.1M) is added and fully mixed, the concentration of isobutene monomer is 35 wt%, 7.5ml of dichloroethylaluminum (0.3M) and 1ml of DCC (0.5M) are taken and mixed to prepare an initiation system, 40ml of hexane is added for dilution and fully mixing, and the mixture is aged for 25min at low temperature. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-20 ℃.
Example 17
1200g of hexane, 646g of isobutene, 43.59g of isoprene and 102.57g of p-tert-butylstyrene are added into a reaction kettle at the temperature of 50 ℃ below zero, 20ml of acetone (0.1M) is added and fully mixed, the concentration of isobutene monomer is 35 wt%, 2ml of titanium tetrachloride (0.4M) and 15mg of HCl gas are taken and mixed to prepare an initiating system, 40ml of hexane is added for dilution and full mixing, and the mixture is aged at low temperature for 25 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-20 ℃.
Example 18
1200g of hexane, 133g of isobutene, 5.30g of isoprene and 15.27g of p-methylstyrene are added into a reaction kettle at the temperature of-50 ℃, 20ml of acetone (0.1M) is added and fully mixed, the concentration of isobutene monomer is 10 wt%, 5.0ml of trichlorotriethylaluminum (0.4M) and 1.2ml of 2-chloro-2, 4, 4-trimethylpentane TMPCl (0.4M) are taken, 40ml of hexane is added for fully mixing, and the mixture is fully diluted and aged at low temperature for 25 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-20 ℃.
Example 19
Adding 600g of hexane, 600g of chloromethane, 133g of isobutene, 5.30g of isoprene and 15.27g of p-methylstyrene into a reaction kettle at the temperature of-40 ℃, adding 10ml of N, N-dimethylformamide (0.1M) into the reaction kettle, and fully mixing the mixture, wherein the concentration of the isobutene monomer is 10 wt%, and taking 5.0ml of trichlorotriethylaluminum (0.4M) and 5.00ml of CH2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for diluting, fully mixing, and aging at low temperature for 30 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-10 ℃.
Example 20
At-40 deg.C, adding hexane 600g, chloromethane 600g, isobutene 133g, isoprene 8.80g and p-methylstyrene 9.16g into reaction kettle, adding 10ml N, N-dimethylformamide (0.1M), mixing thoroughly, the isobutene monomer concentration is 10 wt%, taking 5.0ml trichlorotriethylaluminum (0.4M) and 5.00ml CH2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for diluting, fully mixing, and aging at low temperature for 30 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-10 ℃.
Example 21
At-40 deg.C, adding hexane 600g, chloromethane 600g, isobutene 133g, isoprene 8.80g and p-methylstyrene 9.16g into reaction kettle, adding 10ml N, N-dimethylformamide (0.1M), mixing thoroughly, the isobutene monomer concentration is 10 wt%, taking 5.0ml trichlorotriethylaluminum (0.4M) and 5.00ml CH2Cl2(0.12M) saturated aqueous solution, mixing to prepare an initiation system, adding 40ml of hexane for diluting, fully mixing, and aging at low temperature for 30 min. And (3) pressing the diluted and aged initiator system into a reaction kettle by using nitrogen to initiate polymerization, and adding 20ml of precooled methanol to terminate the reaction when the polymerization temperature rises to-10 ℃.
It should be noted that the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same. It will be understood by those skilled in the art that the present invention may be modified in relation to specific embodiments thereof or may be modified and equivalents may be substituted for elements thereof; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (9)
1. A method of preparing a poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer, characterized in that: aging and complexing a main initiator and a co-initiator into an initiation system, adding an amide as a third component into isobutene, alkylstyrene and isoprene as raw materials, adding the third component into a reactor along with a polymerization monomer during monomer feeding, and preparing a poly (isobutene-co-alkylstyrene-co-isoprene) random copolymer by cationic polymerization in a solvent of methyl chloride and/or hexane, wherein the amount of an alkylstyrene structural unit accounts for 1-5% of the amount of an isobutene structural unit, and the amount of an isoprene structural unit accounts for 1-5% of the amount of the isobutene structural unit; the conversion rate of isobutylene, alkyl styrene and isoprene monomers is 50-100%, and the polymerization temperature is-40 ℃.
2. The method of claim 1, further comprising: the main initiator is one of water, HCl gas, dicumyl chloride (DCC) and 2-chloro-2, 4, 4-Trimethylpentane (TMPCL); the coinitiator is one of alkyl aluminum chloride and titanium tetrachloride; the alkyl aluminum chloride comprises ethyl aluminum dichloride and triethyl aluminum trichloride; the aging time of the main initiator and the co-initiator is 1-30 min.
3. The method of claim 1, further comprising: the alkyl styrene is one of p-methylstyrene, p-ethylstyrene, m-methylstyrene, o-methylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, p-propylstyrene and isopropylstyrene.
4. The method of claim 1, further comprising: the alkylstyrene is p-methylstyrene or p-tert-butylstyrene.
5. The method of claim 1, further comprising: the amide is selected from N, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMA).
6. The method of claim 1, further comprising: the amide is N, N-Dimethylformamide (DMF).
7. The method of claim 1, further comprising: the concentration of the amide as the third component is 1X 10-3～1×10-5mol/L, ratio to main initiator concentration: 0.1 to 10.
8. The method of claim 1, further comprising: the number average molecular weight of the poly (isobutylene-co-alkylstyrene-co-isoprene) random copolymer is 50,000-700,000g/mol, and the molecular weight distribution is 1.2-3.0.
9. The method of claim 1, further comprising: the concentration of the isobutene raw material is 10-35 wt%.
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