CN118271496A - Isoalkenyl terpolymer containing oxygen polar groups and preparation method thereof - Google Patents

Isoalkenyl terpolymer containing oxygen polar groups and preparation method thereof Download PDF

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CN118271496A
CN118271496A CN202211733195.1A CN202211733195A CN118271496A CN 118271496 A CN118271496 A CN 118271496A CN 202211733195 A CN202211733195 A CN 202211733195A CN 118271496 A CN118271496 A CN 118271496A
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terpolymer
styrene
isoolefin
group
monomer
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吴一弦
李思豪
杨诗煊
张丰羽
张树
林金汉
高�正明
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Changzhou Hanwei Polymer Co ltd
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Changzhou Hanwei Polymer Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene

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Abstract

The invention belongs to the technical field of polymer synthesis and material preparation, and relates to an isoolefin terpolymer containing oxygen polar groups and a preparation method thereof. The oxygen-containing polar group isoolefin terpolymer comprises an isoolefin structural unit, a styrene or alkylstyrene structural unit and an oxygen-containing polar group substituted styrene structural unit, wherein the oxygen-containing polar group is selected from at least one of alkanoyloxy, alkoxy and hydroxy. The preparation method comprises the following steps: under the condition of initiator, co-initiator and additive, the above-mentioned three monomers are initiated to make copolymerization reaction, then the terminating agent is added to terminate polymerization reaction, the solvent is removed, and after purification, the above-mentioned three monomers are dried to constant weight so as to obtain the invented ternary copolymer. By adopting the preparation method, the efficient copolymerization reaction of three types of monomers is realized, the copolymerization efficiency is high, the terpolymer is directly synthesized, the molar content of the oxygen-containing polar groups can be more than 2%, the molecular weight distribution is narrower, and the distribution index can reach about 1.5.

Description

Isoalkenyl terpolymer containing oxygen polar groups and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer synthesis and material preparation, and particularly relates to an isoolefin-based terpolymer containing oxygen polar groups and a preparation method thereof.
Background
Polyolefin is a nonpolar bulk polymer material and has wide application fields, but the properties such as printability, dyeing property, hydrophilicity and hydrophobicity, adhesiveness and compatibility with other materials are relatively poor due to the nonpolar characteristic, so that the polar functionalization of polyolefin is always one of important research fields. In order to further improve the comprehensive performance of polyolefin, the introduction of polar groups on the side groups of polyolefin molecular chains is a main technical scheme, and the specific method comprises the following steps: (1) polyolefin post-functionalization; (2) in situ copolymerization of olefins with functionalized monomers. See: chemical notification, 2002,65,527; macromolecular school report 2018,1359; high molecular report 2020,12-29.
Isoolefins are compounds of the family of olefins to which a branched alkyl group is attached at a carbon-carbon double bond carbon, isobutylene being one example. Isobutylene-based polymers such as polyisobutylene or butyl rubber, which are nonpolar polymers, have excellent air tightness, chemical stability, electrical insulation, water resistance, adhesion, etc., and are widely used in oil additives, adhesive materials, sealing materials, anti-corrosive lining materials, etc. Thus, polar functionalization of the isobutylene-based polymer would be advantageous to further enhance the isobutylene-based polymer properties. The preparation of the side group polar functionalized polyisobutene by directly copolymerizing isobutene and polar monomers is the most direct and economic method, and can effectively regulate and control the molecular chain structure of the polyisobutene from the molecular level, but has challenges, and the biggest problems are low polymerization conversion rate, low polymer molecular weight, wide molecular chain distribution and low polar monomer insertion rate. The 3-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate and isobutene are directly copolymerized to obtain the polyisobutenyl copolymer with isocyanate functionalization, but the molecular weight distribution of the copolymerization product is wide. See: journal of Polymer Science Part A Polymer Chemistry,2007,45,4074. Isobutene is copolymerized with styrene derivatives containing pyridine, collidine, thymine and triazole groups, but the copolymerization reaction efficiency is low, and the insertion rate of polar monomers is lower than 2%. See: macromolecules,2010,43,1761; binary copolymerization of isobutene and 4-acetoxystyrene or 4-tert-butoxystyrene, but low copolymerization efficiency and polar monomer insertion rate of less than 1%. See: chinese Journal of Polymer science.2019,37,919; CN107674139a discloses that copolymerization of isobutylene with para-substituted alkyl, aryl or heteroaryl styrenes derivatives (wherein the oxygen atom is not directly linked to the benzene ring in the styrene) gives copolymers of both isobutylene and styrenes derivatives, but with broad molecular weight distribution, and a distribution index of 3.0-8.0.
Disclosure of Invention
The invention aims to provide an oxygen-containing polar group isoolefin-based terpolymer and a preparation method thereof, wherein the oxygen-containing polar group isoolefin-based terpolymer has improved thermal stability, hydrophilicity and adhesiveness, the service life of a material is prolonged, and the interaction with other materials is improved.
In order to achieve the above object, the present invention provides an oxygen-containing polar group-containing isoolefin-based terpolymer comprising an isoolefin structural unit, a styrene or alkyl-substituted styrene structural unit and an oxygen-containing polar group-substituted styrene structural unit;
Wherein the oxygen-containing polar group is at least one selected from alkanoyloxy, alkoxy and hydroxy.
According to the present invention, preferably, the number average molecular weight of the oxygen-containing polar group-containing isoolefin-based terpolymer is 2.0 to 10.0kg/mol, the component distribution index is 1.1 to 2.5, the molar content of the isoolefin structural unit is 40.0 to 97.3%, the molar content of the styrene or alkylstyrene structural unit is 1.0 to 55.0%, and the molar content of the oxygen-containing polar group structural unit is 1.2 to 5.5%, based on the total molar number of structural units in the oxygen-containing isoolefin-based terpolymer.
Preferably, the oxygen-containing polar group-containing isoolefin terpolymer is an alkanoyloxy side group-functionalized isoolefin terpolymer having a number average molecular weight of 2.0 to 8.0kg/mol and a molecular weight distribution index of 1.1 to 2.0, the molar content of isoolefin structural units is 55.0 to 97.3%, the molar content of styrene or alkylstyrene structural units is 1.2 to 43.0%, and the molar content of alkanoyloxy-substituted styrene structural units is 1.4 to 4.5% based on the total number of moles of structural units in the alkanoyloxy side group-functionalized isoolefin terpolymer.
Preferably, the oxygen-containing polar group-containing isoolefin terpolymer is an alkoxy side group functionalized isoolefin terpolymer, the number average molecular weight of the copolymer is 3.0-9.0 kg/mol, the molecular weight distribution index is 1.1-2.0, the molar content of the isoolefin structural units is 40.0-97.0%, the molar content of the styrene or alkylstyrene structural units is 2.0-32.0%, and the molar content of the alkoxy-substituted styrene structural units is 1.2-5.3% based on the total molar number of the structural units in the alkoxy side group functionalized isoolefin terpolymer.
Preferably, the oxygen-containing polar group-containing isoolefin terpolymer is a hydroxyl side group functionalized isoolefin terpolymer, the number average molecular weight of the copolymer is 2.5-12.0 kg/mol, the molecular weight distribution index is 1.1-2.0, the molar content of the isoolefin structural units is 40.0-97.0%, the molar content of the styrene or alkylstyrene structural units is 2.0-55.0%, and the molar content of the hydroxyl-substituted styrene structural units is 1.2-5.3% based on the total molar number of the structural units in the hydroxyl side group functionalized isoolefin terpolymer.
According to the present invention, preferably, the alkanoyloxy group is selected from at least one of formyloxy, acetoxy, propionyloxy, benzoyloxy and phenylacetyloxy; the alkoxy is at least one selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, benzyloxy and phenethyl.
In a second aspect, the present invention provides a process for preparing an isoolefin based terpolymer containing oxygen polar groups comprising the steps of:
(1) Under the protection of inert gas, adding the first monomer, the second monomer, the third monomer and the organic solvent into a polymerization reaction device at the polymerization reaction temperature, and uniformly stirring;
(2) Under stirring, adding an initiator, a co-initiator and an additive to initiate the three monomers to carry out cationic copolymerization reaction;
(3) Adding a terminator to the reaction system to terminate the polymerization reaction, separating out or agglomerating the polymer from the solution by using a non-solvent to remove the solvent, purifying and drying to constant weight to obtain a terpolymer;
The first monomer is isoolefine, the second monomer is alkanoyloxy styrene and/or alkoxy styrene, and the third monomer is selected from styrene and/or styrenealkyl derivatives.
According to the present invention, preferably, the first monomer is an isoolefin having 4 to 8 carbon atoms, preferably at least one selected from the group consisting of isobutene, 2-methyl-1-butene, 2-ethyl-1-butene, 2-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-hexene and 2-ethyl-1-hexene, more preferably isobutene;
The alkanoyloxy styrene is selected from the group consisting of acetoxystyrene, propionyloxy styrene, benzoyloxy styrene, phenylacetoxy styrene, preferably at least one selected from the group consisting of 4-acetoxystyrene, 3-acetoxystyrene, 2-acetoxystyrene, 3, 4-diacetoxy styrene and 3, 5-diacetoxy styrene;
The alkoxyl styrene is at least one selected from methoxystyrene, ethoxystyrene, propoxystyrene, butoxystyrene, pentoxy styrene, hexoxy styrene, heptoxy styrene, octoxy styrene, styrene methoxy styrene and phenethyl oxy styrene, preferably at least one selected from 2-methoxystyrene, 3-methoxystyrene, 4-ethoxystyrene, 2-isopropoxy styrene, 3-tert-butoxy styrene and 4-tert-butoxy styrene;
The third monomer is at least one selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 6-dimethylstyrene, 2, 5-dimethylstyrene, 2, 4-dimethylstyrene, 3, 4-dimethylstyrene, 2,4, 5-trimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,5, 6-tetramethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-propylstyrene, 3-isopropylstyrene, 4-tert-butylstyrene, 1-isobutyl-4-vinylstyrene, 3, 5-diethylstyrene, α -methylstyrene, α -ethylstyrene, 3-methyl- α -methylstyrene, 1-isopropenyl-4-methylstyrene, 1-isopropenyl-3-isopropylbenzene and 1-isopropenyl-4-isopropylbenzene, preferably at least one selected from the group consisting of styrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, α -butylstyrene and α -ethylstyrene;
The molar ratio of the second monomer to the first monomer is (0.008 to 0.60) based on the amount of the substance of the first monomer: 1, preferably (0.009 to 0.55): 1, more preferably (0.01 to 0.52): 1, a step of; third monomer molar ratio of the first monomer (0.008-0.10): 1, preferably (0.009 to 0.08): 1, more preferably (0.01 to 0.06): 1.
In the present invention, the ratio of the amounts of the three monomers to be charged is related to the copolymerization composition of the prepared terpolymer.
According to the present invention, preferably, the initiator is a halogenated hydrocarbon, preferably at least one selected from organic compounds containing a tertiary chlorine group, an allyl chloride group, a benzyl chloride group, a tertiary bromine group, an allyl bromide group and a benzyl bromide group, more preferably at least one selected from tert-butane chloride, allyl bromide, benzyl chloride and benzyl bromide; the molar ratio of the initiator to the monomer is (0.005-0.25): 1, preferably (0.008 to 0.22): 1, more preferably (0.01 to 0.20): 1, a step of;
The co-initiator is a lewis acid, preferably at least one selected from AlCl3、AlEtCl2、Al2Et3Cl3、FeCl3、AlCl3、SnCl4、TiCl4 and ZnCl 2, more preferably at least one selected from AlCl 3、AlEtCl2 and FeCl 3; the molar ratio of the co-initiator to the monomer is (0.01-0.25): 1, preferably (0.02 to 0.20): 1, more preferably (0.03 to 0.18): 1, a step of;
The additive is Lewis base, preferably alcohol compound, more preferably at least one selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, decanol, tridecanol, 2-dimethylpropanol, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethylbutanol, 2-ethylpentanol and 2-ethylhexanol; the molar ratio of the additive to the monomer is (0.01-0.25): 1, preferably (0.02 to 0.24): 1, more preferably (0.03 to 0.23): 1.
In the invention, the amount of the initiator is related to the molecular weight of the polymer to be prepared, the amount of the initiator is high, the formed active center is more, and the molecular weight of the polymer is low; conversely, to obtain a high molecular weight polymer, a low initiator level may be selected; the molar ratio of the initiator to the monomers (the monomers are the sum of the first monomer, the second monomer and the third monomer) is (0.005-0.25): 1, preferably (0.008 to 0.22): 1, more preferably (0.01 to 0.20): 1.
In the invention, the co-initiator is compatible with the initiator to promote the initiator to generate active centers, so that the use amount of the co-initiator is related to the use amount of the initiator. The initiator is high in consumption, and the co-initiator is also required to be used in high consumption; the molar ratio of the co-initiator to the monomer (the monomer is the sum of the first monomer, the second monomer and the third monomer) is (0.01-0.25): 1, preferably (0.02 to 0.20): 1, more preferably (0.03 to 0.18): 1, a step of; the amount of additive is related to the controlled polymerization system, and for better controlled polymerization, a sufficient amount of additive is needed, but too much additive will result in a weaker polymerization, and the molar ratio of the suitable amount of additive to the monomer (the monomer is the sum of the first monomer, the second monomer and the third monomer) is (0.01-0.25): 1, preferably (0.02 to 0.24): 1, more preferably (0.03 to 0.23): 1.
According to the present invention, preferably, the organic solvent is an alkane-based and/or halogenated hydrocarbon-based solvent; the alkane is at least one selected from pentane, hexane, heptane, octane, methylcyclopentane and methylcyclohexane; the halogenated hydrocarbon is at least one selected from methyl chloride, ethyl chloride, chloropropane, chlorobutane, methylene dichloride, dichloroethane and chloroform; preferably, the organic solvent is selected from at least one of methyl chloride, methylene chloride, pentane, hexane, methylcyclopentane, and methylcyclohexane; the terminator is at least one selected from alcohols, ammonia, amines and water, preferably at least one selected from methanol, ethanol and water.
According to the present invention, preferably, the polymerization reaction temperature is-100 to 0 ℃, preferably-90 to-30 ℃; the polymerization time is 5 to 180min, preferably 10 to 120min.
According to the present invention, preferably, optionally, a step of conversion reaction of hydroxyl groups is further included, comprising the steps of:
(1) Dissolving the terpolymer in an aprotic polar solvent to prepare a polymer solution;
(2) Adding a catalyst into the polymer solution to carry out hydrolysis reaction;
(3) And washing with deionized water, standing for layering, precipitating and separating out the polymer in the oil phase, and drying to constant weight to obtain the hydroxyl side group functionalized isoolefin-based terpolymer.
According to the present invention, preferably, the aprotic polar solvent is selected from at least one of tetrahydrofuran, dioxane, and alkane; the alkane is at least one of hexane, cyclohexane and heptane; the catalyst is an acidic catalyst and/or an alkaline catalyst, the acidic catalyst is strong protonic acid, preferably concentrated sulfuric acid, and the alkaline catalyst is sodium alkoxide, preferably sodium methoxide and/or sodium ethoxide;
The temperature of the hydrolysis reaction is 40-80 ℃, preferably 55-65 ℃, and the time of the hydrolysis reaction is 3-24 hours, preferably 5-15 hours.
According to one embodiment of the present invention, preferably, the terpolymer is an alkylacyloxy side-group functionalized isoolefin-based terpolymer, the catalyst is a basic catalyst, and the mass ratio of the catalyst to the alkylacyloxy functional group is (10-1000): 1, preferably (50 to 200): 1, a step of; the aprotic polar solvent is selected from tetrahydrofuran and/or dioxane.
According to another embodiment of the invention, the terpolymer is preferably an alkoxy-functional isoolefin terpolymer, the catalyst is an acidic catalyst, and the mass ratio of the catalyst to the substance of the alkoxy-functional group is preferably (10-1000): 1, more preferably (100 to 200): 1, a step of; the aprotic polar solvent is selected from at least one of tetrahydrofuran, dioxane and alkane; the alkane is at least one of pentane, hexane, cyclohexane, heptane or octane.
The invention has the following beneficial effects:
(1) The efficient copolymerization reaction of introducing the third monomer is realized, and the isoolefin terpolymer with the side group containing alkanoyloxy polar groups and the isoolefin terpolymer with the side group containing alkoxy polar groups are directly synthesized, wherein the molar content of the oxygen-containing polar groups can be more than 2 percent, even more than 5 percent, the molecular weight distribution is narrower, and the distribution index can be about 1.5.
(2) By introducing the third monomer, the monomer polymerization conversion rate is up to more than 90%, the copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the improvement range is up to about 17 times; the copolymerization efficiency of the second polar monomer can be more effectively improved by the high-activity third monomer.
(3) The method is characterized in that the isoolefin terpolymer with the side group containing hydroxyl polar groups is directly and efficiently prepared by further functional group conversion reaction of the isoolefin terpolymer with the side group containing alkanoyloxy polar groups or the isoolefin terpolymer with the side group containing alkoxy polar groups, and the functional group conversion efficiency can reach 100%;
(4) The prepared isoolefin-based terpolymer with the side group containing the oxygen polar group has higher thermal stability, hydrophilicity and adhesiveness, the service life of the material is prolonged, and the interaction with other materials is improved;
(5) The prepared isoolefin-based terpolymer with the side group containing the hydroxyl polar group has good self-repairing performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 shows a self-healing plot after the material of one embodiment of the present invention has been damaged.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
The relative molecular mass and molecular weight distribution of the polymers were determined using a gel permeation chromatograph, designated 1515 by Waters, U.S. Co., ltd., equipped with a 2414 differential refractive detector and a 2487 dual channel UV-visible detector, WATERS STYRAGEL HT, HT4, HT5, and HT 64 gel columns.
The copolymer composition was determined using a 400MHz NMR hydrogen spectrometer AVANCE III (Bruker Co.) at 25℃with deuterated chloroform (CDCl 3) as solvent and Tetramethylsilane (TMS) as standard reference.
Example 1
Adding N-hexane, dichloromethane, isobutene (IB), styrene (St) and 4-Acetoxystyrene (ACS) into a polymerization reactor under the protection of inert gas N 2 and at the temperature of minus 80 ℃ and uniformly mixing. And sequentially adding tert-butyl chloride and a solution containing isopropanol, ferric trichloride and dichloromethane to initiate copolymerization of the three monomers. Wherein the concentration of isobutene is 1mol/L, the volume ratio of normal hexane to dichloromethane is 6/4, and the mole ratios of styrene and 4-acetoxystyrene to isobutene are respectively 0.01:1 and 0.01:1, the molar ratio of tert-butyl chloride to monomer is 0.065:1, and the molar ratios of propanol and ferric trichloride to monomer are respectively 0.072:1 and 0.065:1. after 10min of polymerization, 2mL of pre-cooled ethanol is added to stop the reaction, the polymer is separated out of the solution by using a precipitant, the precipitate is repeatedly dissolved and washed, and the product is placed in a vacuum oven to be dried to constant weight. The IB/St/ACS terpolymer was obtained in a yield of 84.9%.
The results of the test showed that the prepared IB/St/ACS terpolymer had a number average molecular weight (M n) of 6.1kg/mol, a molecular weight distribution index (M w/Mn) of 1.49, a molar content of isobutylene structural units (C IB) of 97.27%, a molar content of styrene structural units (C St) of 1.31% and a molar content of ACS structural units (C ACS) of 1.42%.
The prepared IB/St/ACS terpolymer is a hydrophobic polymer, and the water contact angle of the surface of the material is 101 degrees; the prepared IB/St/ACS terpolymer has excellent thermal stability, and the decomposition temperature (T d,5％) at the weight loss of 5% is 381 ℃.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 84.9%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 1.42mol percent by 4.07 times;
(3) The surface hydrophilicity of the IB/St/ACS terpolymer is improved, and the water contact angle is reduced by 11 degrees;
(4) The thermal stability of the terpolymer is improved, and T d,5％ is increased by 15 ℃.
Example 2
The synthesis of IB/St/ACS terpolymers was the same as in example 1 except that the molar ratio of St to IB was 0.1:1, the molar ratio of ACS to IB was 0.05:1, the molar ratio of tert-butyl chloride to monomer was 0.057:1, and the molar ratio of isopropyl alcohol to monomer was 0.063:1, the molar ratio of ferric trichloride to monomer is 0.057:1. the yield of IB/St/ACS terpolymer was 89.4%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 4.1kg/mol, M w/Mn of 1.61, C IB of 91.90%, C St of 6.57% and C ACS of 1.53%. The prepared IB/St/ACS terpolymer has excellent heat stability, and the T d,5％ is 380 ℃.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 89.4%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 1.53mol percent by 4.46 times;
(3) The thermal stability of the terpolymer is improved, and the temperature of T d,5％ is increased by 14 ℃.
Example 3
The synthesis of IB/St/ACS terpolymers was the same as in example 1 except that the molar ratio of St to IB was 0.2:1, the molar ratio of ACS to IB was 0.05:1, the molar ratio of tert-butyl chloride to monomer was 0.053:1, and the molar ratio of isopropyl alcohol to monomer was 0.058:1, the molar ratio of ferric trichloride to monomer is 0.053:1. the yield of IB/St/ACS terpolymer was 92.3%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 3.6kg/mol, M w/Mn of 1.51, C IB of 80.80%, C St of 17.4% and C ACS of 1.80%.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 92.3%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 1.80mol percent by 5.42 times.
Example 4
The IB/St/ACS terpolymer was synthesized in the same manner as in example 1, and the amounts of the polar monomer and the third monomer styrene charged in the reaction system were the same as in example 3, except that the polymerization temperature was-60 ℃. The yield of IB/St/ACS terpolymer was 72.1%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 3.5kg/mol, M w/Mn of 1.88, C IB of 80.78%, C St of 17.3mol% and C ACS of 1.92mol%.
Compared with example 3, the polymerization temperature is increased, the copolymer yield is reduced, but the second monomer participates in the copolymerization efficiency is improved, and the copolymerization composition content of the second polar monomer ACS in the prepared terpolymer is improved by 6.7%.
Example 5
The synthesis method of IB/St/ACS terpolymer was the same as in example 1, and the amounts of the polar monomer and the third monomer styrene charged in the reaction system were the same as in example 3, except that the polymerization temperature was increased to-40 ℃. The yield of IB/St/ACS terpolymer was 33.7%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 2.2kg/mol, M w/Mn of 1.62, C IB of 57.08%, C St of 40.9% and C ACS of 2.02%.
Compared with example 3, the polymerization temperature is increased, the copolymer yield is reduced, but the second monomer participates in the copolymerization efficiency is improved, and the copolymerization composition content of the second polar monomer ACS in the prepared terpolymer is improved by 12.2%.
Example 6
The synthesis method of IB/St/ACS terpolymer is the same as in example 1, except that in the reaction system, the charged amounts of the polar monomer and styrene are different, the molar ratio of St to IB is 0.3:1, the molar ratio of ACS to IB is 0.05:1, the molar ratio of chlorobutane to monomer is 0.049:1, and the molar ratio of isopropanol to monomer is 0.054:1, the molar ratio of ferric trichloride to monomer is 0.049:1. the yield of IB/St/ACS terpolymer was 93.5%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 4.0kg/mol, M w/Mn of 1.59, C IB of 67.60%, C St of 29.70% and C ACS of 2.70mol%.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 93.5%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 2.70mol percent by 8.64 times.
Example 7
The synthesis method of IB/St/ACS terpolymer is the same as in example 2, except that in the reaction system, the charged amounts of the polar monomer and styrene are different, the molar ratio of St to IB is 0.4:1, the molar ratio of ACS to IB is 0.05:1, the molar ratio of chlorobutane to monomer is 0.046:1, and the molar ratio of isopropanol to monomer is 0.050:1, the molar ratio of ferric trichloride to monomer is 0.046:1. the yield of IB/St/ACS terpolymer was 94.2%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 4.5kg/mol, M w/Mn of 1.51, C IB of 57.77%, C St of 38.10% and C ACS of 4.13%.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 94.2%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 4.13mol percent, and is improved by 13.75 times.
Example 8
The synthesis method of IB/St/ACS terpolymer is the same as in example 2, except that in the reaction system, the charged amounts of the polar monomer and styrene are different, the molar ratio of St to IB is 0.5:1, the molar ratio of ACS to IB is 0.05:1, the molar ratio of chlorobutane to monomer is 0.043:1, and the molar ratio of isopropanol to monomer is 0.047:1, the molar ratio of ferric trichloride to monomer is 0.043:1. the yield of IB/St/ACS terpolymer was 89.6%.
The test results showed that the prepared IB/St/ACS terpolymer had M n of 3.6kg/mol, M w/Mn of 1.64, C IB of 40.53%, C St of 54.3% and C ACS of 5.17%.
In comparison with comparative example 1, it can be derived that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 22.5% to 89.6%;
(2) The copolymerization efficiency of the ACS of the second polar monomer is greatly improved, and the copolymerization composition content of the ACS in the terpolymer is improved from 0.28mol percent to 4.13mol percent by 17.46 times.
Example 9
The synthesis of IB/St/TBO terpolymers was the same as in example 1 except that the second monomer was 4-t-butoxystyrene (TBO), the molar ratios of styrene and 4-t-butoxystyrene to isobutylene were 0.05:1 and 0.02:1, respectively, the molar ratio of chlorobutane to monomer was 0.011:1, and the molar ratio of isopropanol to monomer was 0.071:1, the molar ratio of ferric trichloride to monomer is 0.059:1 propanol. After 40min of polymerization. The IB/St/TBO terpolymer was obtained in a yield of 74.6%.
The test results showed that the IB/St/TBO terpolymer prepared had a M n of 7.0kg/mol and a M w/Mn of 1.51, wherein C IB was 96.66%, C St was 2.10% and TBO structural unit molar content (C TBO) was 1.24%.
The prepared IB/St/TBO terpolymer is a hydrophobic polymer, and the water contact angle of the surface of the material is 112 degrees; the prepared IB/St/TBO terpolymer has excellent thermal stability, and T d,5％ is 372 ℃.
Compared to comparative example 2, it can be obtained that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 21.1% to 74.6%;
(2) The copolymerization efficiency of the TBO of the second polar monomer is greatly improved, and the copolymerization composition content of the TBO in the terpolymer is improved from 0.38mol% to 1.24mol%, which is improved by 2.26 times;
(3) The thermal stability of the terpolymer is improved, and T d,5％ is increased by 13 ℃.
Example 10
The synthesis of IB/St/TBO terpolymers was performed as in example 9, except that the molar ratio of TBO to IB was 0.05:1, the molar ratio of tert-butyl chloride to monomer was 0.178:1, and the molar ratio of isopropyl alcohol to monomer was 0.224:1, the molar ratio of ferric trichloride to monomer is 0.160:1. the yield of IB/St/TBO terpolymer was 75.7%.
The test results showed that the prepared IB/St/TBO terpolymer had an M n of 3.1kg/mol, an M w/Mn of 1.49, a C IB of 95.44%, a C St of 2.58% and a C TBO of 1.98%.
The prepared IB/St/TBO terpolymer is a hydrophobic polymer, and the water contact angle of the surface of the material is 114.5 degrees; the prepared IB/St/TBO terpolymer has excellent thermal stability, and T d,5％ is 368 ℃.
Compared to comparative example 2, it can be obtained that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 21.1% to 75.7%;
(2) The copolymerization efficiency of the TBO of the second polar monomer is greatly improved, and the copolymerization composition content of the TBO in the terpolymer is improved from 0.38mol% to 1.98mol%, which is improved by 4.21 times;
(3) The thermal stability of the terpolymer is improved, and the temperature T d,5％ is increased by 9 ℃.
Example 11
IB/MS/TBO terpolymer was synthesized as in example 10 except that styrene (St) was replaced with an equimolar amount of 4-Methylstyrene (MS) and polymerized for 130 minutes. IB/MS/TBO terpolymer 86.3%
The test results showed that the prepared IB/MS/TBO terpolymer had M n of 3.8kg/mol, M w/Mn of 1.49, C IB of 64.85%, and MS structural unit molar content (C MS) of 31.82% and C TBO of 3.33%.
Compared to comparative example 2, it can be obtained that:
(1) By introducing the third monomer, the polymerization efficiency is obviously improved, and the copolymer yield is greatly improved from 21.1% to 86.3%;
(2) The copolymerization efficiency of the TBO of the second polar monomer is greatly improved, and the copolymerization composition content of the TBO in the terpolymer is improved from 0.38mol% to 3.33mol%, which is improved by 7.76 times;
In comparison with example 10, it can be derived that: by introducing the high-activity third monomer, the copolymerization efficiency of the second monomer is improved, the copolymer yield is further improved, and the TBO copolymerization composition is also improved by 66.7%.
Example 12
50Mg of the IB/St/ACS terpolymer prepared in example 4 was dissolved in 20mL of THF solvent to prepare a polymer solution. Sodium methoxide was added to the reaction system and reacted at 60℃for 16 hours. Washing with deionized water for several times to neutrality after the reaction, standing for layering, precipitating polymer in the oil phase, and drying in a vacuum oven to constant weight.
The test result shows that the characteristic peak of the lateral group acetoxyl group in the IB/St/ACS terpolymer completely disappears, other structural units are kept unchanged, and the IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group is prepared, wherein C IB is 80.78%, C St is 17.30%, and the molar content of the 4-hydroxystyrene structural unit (C POH) is 1.92%.
Example 13
50Mg of the IB/St/ACS terpolymer prepared in example 6 was dissolved in 20mL of THF solvent to prepare a polymer solution. Sodium methoxide was added to the reaction system and reacted at 60℃for 24 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the lateral group acetoxy group in the IB/St/ACS terpolymer completely disappears, other structural units are kept unchanged, and the IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group is prepared, wherein the C IB is 67.60%, the C St is 29.70%, and the C POH is 2.70%.
Example 14
50Mg of the IB/St/ACS terpolymer prepared in example 7 was dissolved in 20mL of THF solvent to prepare a polymer solution. Sodium methoxide was added to the reaction system and reacted at 60℃for 24 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the lateral group acetoxy group in the IB/St/ACS terpolymer completely disappears, other structural units remain unchanged, and the IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group is prepared, wherein the C IB is 57.77%, the C St is 38.1%, and the C POH is 4.13%.
Example 15
50Mg of the IB/St/ACS terpolymer prepared in example 8 was dissolved in 20mL of THF solvent to prepare a polymer solution. Sodium methoxide was added to the reaction system and reacted at 60℃for 24 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the lateral group acetoxy group in the IB/St/ACS terpolymer completely disappears, other structural units remain unchanged, and the IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group is prepared, wherein C IB is 40.53%, C St is 54.30%, and C POH is 5.17%.
Example 16
2.0G of the IB/St/TBO terpolymer prepared in example 9 was dissolved in a mixed solvent of 60mL of THF and 40mL of n-hexane to prepare a polymer solution. 1mL of H 2SO4 was added to the reaction system, and the mixture was reacted at 60℃for 20 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the lateral group tertiary butoxy group in the IB/St/TBO terpolymer completely disappears, other structural units remain unchanged, and the IB/St/POH terpolymer with the lateral group containing hydroxyl polar group is prepared, wherein: c IB was 96.66%, C St was 2.10%, and C POH was 1.24%. The prepared IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group has excellent thermal stability, and the T d,5％ is 372 ℃.
The prepared IB/St/POH terpolymer with the side group containing the hydroxyl polar group has excellent self-repairing performance, and after the surface of the material is scratched and destroyed, the total self-repairing is realized at room temperature for 80min as shown in figure 1.
Example 17
A polymer solution was prepared by dissolving 0.6g of the IB/St/TBO terpolymer prepared in example 10 in a mixed solvent of 30mL of THF and 20mL of n-hexane. 1mL of HCl was added to the reaction system, and the mixture was reacted at 60℃for 18 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the lateral group tertiary butoxy group in the IB/St/TBO terpolymer completely disappears, other structural units remain unchanged, and the IB/St/POH terpolymer with the lateral group containing the hydroxyl polar group is prepared, wherein the C IB is 95.44%, the C St is 2.58%, and the C POH is 1.98%.
The prepared IB/St/POH terpolymer with the lateral group containing hydroxyl is a hydrophilic polymer, the water contact angle of the material surface is 96.3 degrees, and the hydrophilicity is further improved; the prepared IB/St/POH terpolymer with the lateral group containing hydroxyl has excellent thermal stability, and the T d,5％ is 368.1 ℃.
Example 18
A polymer solution was prepared by dissolving 0.6g of the IB/MS/TBO terpolymer prepared in example 11 in a mixed solvent of 30mL of THF and 20mL of n-hexane. 1mL of HCl was added to the reaction system, and the mixture was reacted at 60℃for 26 hours. The post-treatment procedure was as in example 12.
The test result shows that the characteristic peak of the side group tertiary butoxy group in the IB/MS/TBO terpolymer completely disappears, other structural units remain unchanged, and the IB/MS/POH terpolymer with the side group containing the hydroxyl polar group is prepared, wherein C IB is 64.85%, C MS is 31.82%, and C POH is 3.33%.
Comparative example 1
The experimental procedure and conditions were the same as in example 1, except that: styrene (St) was not added and the molar ratio of 4-Acetoxystyrene (ACS) to isobutylene was 0.02:1. The yield of the produced copolymer was 22.5%, M n was 8.0kg/mol, M w/Mn was 1.49 and C ACS was 0.28%.
The decomposition temperature (T d,5％) of the IB/ACS binary copolymer at 5% weight loss is 366 ℃; the IB/ACS binary copolymer is a hydrophobic polymer, and the water contact angle of the material surface is 112 degrees.
Comparative example 2
The experimental procedure and conditions were the same as in example 9, except that: styrene (St) was not added and the molar ratio of 4-t-butoxystyrene (TBO) to isobutylene was 0.05:1. The produced copolymer yield was 21.1%, M n was 13kg/mol, M w/Mn was 1.5, and C TBO was 0.38mol%.
The 5% weight loss temperature of the IB/TBO binary copolymer is 359 ℃; the IB/TBO binary copolymer is a hydrophobic polymer, and the water contact angle of the material surface is 109 degrees.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (10)

1. An oxygen-containing polar group-containing isoolefin terpolymer characterized in that the oxygen-containing polar group-containing isoolefin terpolymer comprises an isoolefin structural unit, a styrene or alkyl-substituted styrene structural unit, and an oxygen-containing polar group-substituted styrene structural unit;
Wherein the oxygen-containing polar group is at least one selected from alkanoyloxy, alkoxy and hydroxy.
2. The oxygen-containing polar group-containing isoolefin terpolymer according to claim 1, wherein the oxygen-containing polar group-containing isoolefin terpolymer has a number average molecular weight of 2.0 to 10.0kg/mol, a component distribution index of 1.1 to 2.5, a molar content of the isoolefin structural unit of 40.0 to 97.3% and a molar content of the styrene or alkylstyrene structural unit of 1.0 to 55.0% based on the total molar number of structural units in the oxygen-containing polar group-containing isoolefin terpolymer, and a molar content of the oxygen-containing polar group structural unit of 1.2 to 5.5%;
Preferably, the oxygen-containing polar group-functionalized isoolefin-based terpolymer is an alkanoyloxy side group-functionalized isoolefin-based terpolymer, the number average molecular weight of the copolymer is 2.0-8.0 kg/mol, the molecular weight distribution index is 1.1-2.0, the molar content of the isoolefin-based structural units is 55.0-97.3%, the molar content of the styrene or alkylstyrene structural units is 1.2-43.0%, and the molar content of alkanoyloxy-substituted styrene structural units is 1.4-4.5% based on the total molar number of structural units in the alkanoyloxy side group-functionalized isoolefin-based terpolymer;
Preferably, the oxygen-containing polar group-containing isoolefin terpolymer is an alkoxy side group functionalized isoolefin terpolymer, the number average molecular weight of the copolymer is 2.0-9.0 kg/mol, the molecular weight distribution index is 1.1-2.0, the molar content of the isoolefin structural units is 40.0-97.0%, the molar content of the styrene or alkylstyrene structural units is 2.0-32.0%, and the molar content of the alkoxy-substituted styrene structural units is 1.2-5.3% based on the total molar number of the structural units in the alkoxy side group functionalized isoolefin terpolymer;
Preferably, the oxygen-containing polar group-containing isoolefin terpolymer is a hydroxyl side group functionalized isoolefin terpolymer, the number average molecular weight of the copolymer is 2.0-9.0 kg/mol, the molecular weight distribution index is 1.1-2.5, the molar content of the isoolefin structural units is 40.0-97.0%, the molar content of the styrene or alkylstyrene structural units is 2.0-55.0%, and the molar content of the hydroxyl-substituted styrene structural units is 1.2-5.3% based on the total molar number of the structural units in the hydroxyl side group functionalized isoolefin terpolymer.
3. The oxygen-containing polar group-containing isoolefin terpolymer of claim 1, wherein the alkanoyloxy group is selected from at least one of formyloxy, acetoxy, propionyloxy, benzoyloxy, and phenylacetyloxy; the alkoxy is at least one selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, benzyloxy and phenethyl.
4. A process for the preparation of an isoolefin based terpolymer containing oxygen polar groups according to any one of claims 1 to 3 comprising the steps of:
(1) Under the protection of inert gas, adding a first monomer, a second monomer, a third monomer and an organic solvent into a polymerization reaction device at the polymerization reaction temperature, and uniformly stirring;
(2) Under stirring, adding an initiator, a co-initiator and an additive to initiate the three monomers to carry out cationic copolymerization reaction;
(3) Adding a pre-cooled terminator into a reaction system to terminate the polymerization reaction, separating out or agglomerating a polymer from the solution by using a non-solvent to remove the solvent, purifying, and drying to constant weight to obtain a terpolymer;
the first monomer is isoolefine, the second monomer is alkanoyloxy styrene and/or alkoxy styrene, and the third monomer is styrene and/or styrenealkyl derivative.
5. The process for producing an isoolefin based terpolymer containing oxygen polar group according to claim 4, wherein the first monomer is an isoolefin having 4 to 8 carbon atoms, preferably at least one selected from the group consisting of isobutylene, 2-methyl-1-butene, 2-ethyl-1-butene, 2-methyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-1-hexene and 2-ethyl-1-hexene, more preferably isobutylene;
The alkanoyloxy styrene is selected from the group consisting of acetoxystyrene, propionyloxy styrene, benzoyloxy styrene, phenylacetoxy styrene, preferably at least one selected from the group consisting of 4-acetoxystyrene, 3-acetoxystyrene, 2-acetoxystyrene, 3, 4-diacetoxy styrene and 3, 5-diacetoxy styrene;
the alkoxyl styrene is at least one selected from methoxystyrene, ethoxystyrene, propoxystyrene, butoxystyrene, pentoxy styrene, hexoxy styrene, heptoxy styrene, octoxy styrene, styrene methoxy styrene and phenethyl oxy styrene, preferably at least one selected from 2-methoxystyrene, 3-methoxystyrene, 4-ethoxystyrene, 2-isopropoxy styrene, 3-tert-butoxy styrene and 4-tert-butoxy styrene; the third monomer is at least one selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 6-dimethylstyrene, 2, 5-dimethylstyrene, 2, 4-dimethylstyrene, 3, 4-dimethylstyrene, 2,4, 5-trimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,5, 6-tetramethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-propylstyrene, 3-isopropylstyrene, 4-tert-butylstyrene, 1-isobutyl-4-vinylstyrene, 3, 5-diethylstyrene, α -methylstyrene, α -ethylstyrene, 3-methyl- α -methylstyrene, 1-isopropenyl-4-methylstyrene, 1-isopropenyl-3-isopropylbenzene and 1-isopropenyl-4-isopropylbenzene, preferably at least one selected from the group consisting of styrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, α -butylstyrene and α -ethylstyrene;
The molar ratio of the second monomer to the first monomer is (0.008 to 0.60) based on the amount of the substance of the first monomer: 1, preferably (0.009 to 0.55): 1, more preferably (0.01 to 0.52): 1, a step of; third monomer molar ratio of the first monomer (0.008-0.10): 1, preferably (0.009 to 0.08): 1, more preferably (0.01 to 0.06): 1.
6. The process for producing an oxygen-containing polar group-containing isoolefin terpolymer according to claim 4, wherein the initiator is a halogenated hydrocarbon, preferably at least one selected from the group consisting of an organic compound containing a tertiary chlorine group, an allyl chloride group, a benzyl chloride group, a tertiary bromine group, an allyl bromide group and a benzyl bromide group, more preferably at least one selected from the group consisting of tert-butane chloride, allyl bromide, benzyl chloride and benzyl bromide; the molar ratio of the initiator to the monomer is (0.005-0.25): 1, preferably (0.008 to 0.22): 1, more preferably (0.01 to 0.20): 1, a step of;
The co-initiator is a lewis acid, preferably at least one selected from AlCl3、AlEtCl2、Al2Et3Cl3、FeCl3、AlCl3、SnCl4、TiCl4 and ZnCl 2, more preferably at least one selected from AlCl 3、AlEtCl2 and FeCl 3; the molar ratio of the co-initiator to the monomer is (0.01-0.25): 1, preferably (0.02 to 0.20): 1, more preferably (0.03 to 0.18): 1, a step of;
The additive is Lewis base, preferably alcohol compound, more preferably at least one selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, decanol, tridecanol, 2-dimethylpropanol, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethylbutanol, 2-ethylpentanol and 2-ethylhexanol; the molar ratio of the additive to the monomer is (0.01-0.25): 1, preferably (0.02 to 0.24): 1, more preferably (0.03 to 0.23): 1.
7. The method for producing an oxygen-containing polar group-containing isoolefin-based terpolymer according to claim 4, wherein the organic solvent is an alkane-based and/or halogenated hydrocarbon-based solvent; the alkane is at least one selected from pentane, hexane, heptane, octane, methylcyclopentane and methylcyclohexane; the halogenated hydrocarbon is at least one selected from methyl chloride, ethyl chloride, chloropropane, chlorobutane, methylene dichloride, dichloroethane and chloroform; preferably, the organic solvent is selected from at least one of methyl chloride, methylene chloride, pentane, hexane, methylcyclopentane, and methylcyclohexane; the terminator is at least one selected from alcohols, ammonia, amines and water, preferably at least one selected from methanol, ethanol and water.
8. The method for producing an oxygen-containing polar group-containing isoolefin terpolymer according to claim 4, wherein the polymerization reaction temperature is-100 to 0 ℃, preferably-90 to-30 ℃; the polymerization time is 5 to 180min, preferably 10 to 120min.
9. The method for producing an oxygen-containing polar group-containing isoolefin terpolymer according to any one of claims 4 to 8, wherein, optionally, a conversion reaction step of a hydroxyl group is further included, comprising the steps of:
(1) Dissolving the terpolymer in an aprotic polar solvent to prepare a polymer solution;
(2) Adding a catalyst into the polymer solution to carry out hydrolysis reaction;
(3) And washing with deionized water, standing for layering, precipitating and separating out the polymer in the oil phase, and drying to constant weight to obtain the hydroxyl side group functionalized isoolefin-based terpolymer.
10. The method for producing an oxygen-containing polar group-containing isoolefin terpolymer according to claim 9, wherein the aprotic polar solvent is selected from at least one of tetrahydrofuran, dioxane and alkane; the alkane is at least one of hexane, cyclohexane and heptane; the catalyst is an acidic catalyst and/or an alkaline catalyst, the acidic catalyst is strong protonic acid, preferably concentrated sulfuric acid, and the alkaline catalyst is sodium alkoxide, preferably sodium methoxide and/or sodium ethoxide;
the hydrolysis reaction temperature is 40-80 ℃, preferably 55-65 ℃ for 3-24 hours, preferably 5-15 hours;
Preferably, the terpolymer is alkanoyloxy side group functionalized isoolefin terpolymer, the catalyst is a basic catalyst, and the mass ratio of the catalyst to the alkanoyloxy functional group is (10-1000): 1, preferably (50 to 200): 1, a step of; the aprotic polar solvent is selected from tetrahydrofuran and/or dioxane;
preferably, the terpolymer is an alkoxy-functional isoolefin terpolymer, the catalyst is an acidic catalyst, and the mass ratio of the catalyst to the substance of the alkoxy functional group is preferably (10-1000): 1, more preferably (100 to 200): 1, a step of; the aprotic polar solvent is selected from at least one of tetrahydrofuran, dioxane and alkane; the alkane is at least one of pentane, hexane, cyclohexane, heptane or octane.
CN202211733195.1A 2022-12-30 2022-12-30 Isoalkenyl terpolymer containing oxygen polar groups and preparation method thereof Pending CN118271496A (en)

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