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CN111320717B - A method for catalyzing the polymerization of vinyl monomers based on the hindered Lewis acid-base pair of dinuclear aluminum Lewis acids - Google Patents

A method for catalyzing the polymerization of vinyl monomers based on the hindered Lewis acid-base pair of dinuclear aluminum Lewis acids Download PDF

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CN111320717B
CN111320717B CN202010172280.XA CN202010172280A CN111320717B CN 111320717 B CN111320717 B CN 111320717B CN 202010172280 A CN202010172280 A CN 202010172280A CN 111320717 B CN111320717 B CN 111320717B
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CN111320717A (en
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王晓武
王哲
咸漠
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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Abstract

The invention discloses a method for catalyzing vinyl monomer polymerization by using a hindered Lewis acid-base pair based on binuclear aluminum Lewis acid, belonging to the technical field of polymer synthesis. The invention realizes the high-efficiency catalysis of the vinyl monomer under mild conditions, and the molecular weight and molecular weight distribution of the polymer are controllable, thereby providing a new strategy and method for the controllable synthesis of the polymer. The polymerization mechanism in the invention relates to the conjugated addition of binuclear aluminum under the synergistic catalytic action. The binuclear aluminum catalytic system has the advantages of low price, easy obtaining, convenient operation, mild reaction conditions, wide monomer adaptability and the like. In addition, the high-efficiency conversion of different monomers can be realized by adjusting the pKa of Lewis acid/alkali, the molecular weight and the molecular weight distribution of the polymer can be accurately regulated, and the initiation efficiency is close to 100 percent. The catalytic system can efficiently catalyze homopolymerization and copolymerization of methyl methacrylate and butyl acrylate, and provides a new synthesis strategy and approach for copolymer thermoplastic elastomers of methyl methacrylate and butyl acrylate.

Description

Method for catalyzing vinyl monomer polymerization by using hindered Lewis acid-base pair based on binuclear aluminum Lewis acid
Technical Field
The invention relates to a method for catalyzing vinyl monomer polymerization by using a hindered Lewis acid-base pair based on binuclear aluminum Lewis acid, belongs to the technical field of high molecular synthesis, and particularly relates to a preparation method of binuclear organic metal aluminum Lewis acid and an active polymerization system for catalyzing vinyl polar monomers to synthesize high molecular weight polymers.
Background
Polymethyl methacrylate, commonly known as polymethyl methacrylate (PMMA), is a transparent organic polymer material. Because of its unique physical and chemical properties, it has the advantages of light weight, easy processing, good transparency and resistance, etc., and can be extensively used in the fields of automobile, building and medicine, etc. At present, the demand of PMMA in China is increasing day by day, but the PMMA production technology is mainly mastered by enterprises in developed countries such as the United states, Japan and the like, and the demand of high-quality PMMA in China depends on import. Therefore, it is necessary to develop a technology for improving the properties of PMMA in order to get rid of the monopoly of PMMA with high quality abroad and meet the domestic demand for PMMA. Meanwhile, thermoplastic elastomers based on PMMA are also the best substitute for styrene elastomers.
The Lewis acid base pair in the existing catalyst for catalyzing polar vinyl monomer polymerization can obtain a catalyst with narrower molecular weight distribution under mild conditions, and can selectively catalyze and polymerize a non-polar diene region, so that double bonds of monomers in the obtained polymer can be completely reserved. However, most of the existing Lewis acid-base pairs have the defects of low initiation efficiency, incomplete monomer conversion, incapability of obtaining polymers with high molecular weight and narrow molecular weight distribution simultaneously and concomitant side reactions of chain transfer and chain termination in the polymerization process in the process of catalyzing the polymerization of polar vinyl monomers. In addition, the current research is mostly a mononuclear aluminum Lewis acid system, and a binuclear aluminum Lewis acid-based catalytic system is not reported. The method is based on design synthesis of binuclear aluminum Lewis acid and design of Lewis acid-base pairs thereof, provides a new polymerization strategy and method for vinyl polar monomers, can effectively inhibit side reactions by a double-channel Lewis acid center, provides possibility for homopolymerization and copolymerization experiments of polar monomers, and provides a new strategy and way for realizing synthesis of PMMA thermoplastic elastomers under mild conditions.
Disclosure of Invention
The invention introduces dual-core Lewis acid, improves the initiation efficiency of MMA and nBA monomers, inhibits side reaction to realize the high-efficiency controllable synthesis of PMMA and PnBA, and provides a new strategy and approach for the synthesis of PMMA thermoplastic elastomer under mild conditions. And provides a method for polymerizing other vinyl monomers by using hindered Lewis acid base based on binuclear aluminum Lewis acid.
The technical scheme of the invention is as follows:
a method for catalyzing vinyl monomer polymerization by using a hindered Lewis acid-base pair based on binuclear aluminum Lewis acid is characterized in that a vinyl polar monomer is used as a raw material of the monomer in an organic solvent at room temperature, a conjugate addition polymerization reaction is carried out under the catalysis of the hindered Lewis acid-base pair consisting of binuclear aluminum Lewis acid and Lewis base, the polymerization time is 1s-2h, and the quenching is carried out after the reaction is finished.
Further limiting, the structural formula of the binuclear aluminum Lewis acid is as follows:
Figure BDA0002409604390000021
in the formula, R1Is tert-butyl or 1-methylcyclohexyl, R2Is methyl or tert-butyl, R3Is methyl, ethyl or Cl.
Further defined, the Lewis base is an organophosphorus, carbene, or phosphine base.
More particularly, the carbene has the structural formula:
Figure BDA0002409604390000022
wherein R is methyl, ethyl, isopropyl, tert-butyl or 2,4, 6-trimethylphenyl.
More particularly, the organic phosphorus has the formula:
Figure BDA0002409604390000023
wherein R is1Is methyl, ethyl, phenyl, cyclohexyl, 4-methoxyphenyl, 4-methylphenyl, tert-butyl or n-butyl.
Further defined, the vinyl polar monomer has the formula:
Figure BDA0002409604390000024
wherein R is1Is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl, R2Is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl.
Further limit, the organic solvent is one or more than two of toluene, tetrahydrofuran, hexane and dichloromethane which are mixed in any proportion, and the concentration of the vinyl monomer in the organic solvent is 1mol/L-10 mol/L.
Further limit, the mol ratio of the vinyl polar monomer, the binuclear aluminum Lewis acid and the Lewis base is (200-3200) (1-5) to (1-5).
Further limit is as follows: the quenching agent is a methanol solution containing BHT, and the mass fraction of the BHT is 5-10%.
More particularly, the molar ratio of quencher to hindered lewis acid-base pair is 1: 1.
the invention has the following beneficial effects: the invention uses binuclear organic aluminum metal complex as Lewis acid, and under the synergistic action of Lewis base, the binuclear organic aluminum metal complex and polar vinyl monomer form active species, and another Lewis acid center is reserved, thereby improving the catalytic activity and inhibiting the phenomenon of back biting. In the polymerization process, the active species can not only rapidly realize homopolymerization active polymerization; and can realize the block copolymerization among different vinyl polar monomers, in particular the block copolymerization or the random copolymerization among methacrylic esters, thereby obtaining high polymer materials with different properties. The molecular weight of the obtained polymer is in direct proportion to the molar ratio of the monomer to the catalyst, the polymers with different molecular weights can be obtained by adjusting the molar ratio of the monomer to the catalyst, and even the molecular weight of the ultra-high molecular weight polymer can reach 2 x 106The molecular weight of the obtained polymer is consistent with a theoretical value and the molecular weight distribution is narrow at the level of more than g/mol.
In summary, the beneficial technical effects obtained by the invention are summarized as follows:
(1) the binuclear catalytic system of the present invention has cheap material and no noble metal.
(2) The invention designs the method which takes aluminum as a binuclear Lewis acid center and forms a large-site blocked Lewis acid with a ligand to improve
Catalytic activity, when accelerating polymerization, complete conversion of monomer (monomer and catalyst) can be completed within 2 minutes
The molar ratio can reach 3200: 1).
(3) The catalytic system of the invention can accurately regulate and control the molecular weight of the polymer, and the molecular weight distribution is narrow (<1.2),
the initiation efficiency is close to 100%, and the actual molecular weight is close to the theoretical molecular weight.
(4) The catalytic system of the invention can realize methyl methacrylate, butyl acrylate and other polar vinyl
The activity of the monomer can be controlled and polymerized, and the block copolymerization of methyl methacrylate and butyl acrylate can be realized
Homopolymerization and copolymerization of other polar vinyl monomers.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The structure and numbering of the binuclear aluminum Lewis acid used in the following examples are as follows:
[Al(mbmp)Me]2is composed of
Figure BDA0002409604390000041
Wherein R is1Is tert-butyl, R2Is methyl, R3Is methyl.
The structure and numbering of Lewis bases is as follows:
tBuIm：
Figure BDA0002409604390000042
MesIm：
Figure BDA0002409604390000043
iPrIm：
Figure BDA0002409604390000044
wherein R is1Cyclohexyl, ethyl, phenyl, 4-methoxyphenyl or 4-methylphenyl.
Example 1
In a glove box, a specified amount of Lewis acid ([ Al (mbmp) Me) was added to a Schlenk flask]2) MMA, in the amounts indicatedThen 2mL of toluene solution was added, the mixture was stirred well, and then a prescribed amount of Lewis base (II) was added to the flaskiPrIm) After the addition, the reaction was started, after the reaction was completed, the Schlenk bottle was taken out from the glove box, quenched by adding a methanol solution containing 5% BHT, 0.2mL of the solution was taken out in deuterated chloroform to measure nuclear magnetism, the remaining liquid was extracted with a large amount of methanol, the solid was taken out, dried in a vacuum drying oven at 40 ℃ to constant weight, the conversion rate was calculated from the nuclear magnetism result, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 1 treatment with basesiPrIm) The polymerization results obtained as Lewis base under different reaction conditions are shown in the table below
Figure BDA0002409604390000045
By designing the proportion of different monomers to the catalyst, the linear increase of the conversion rate along with time and the linear increase of the molecular weight along with the conversion rate are observed, and meanwhile, the molecular weight distribution PDI keeps narrow distribution, so that the reaction can be effectively proved to be controllable living polymerization. Example 2
The reaction was carried out in a glovebox and 0.024mmol of Lewis acid ([ Al (mbmp) Me) was added to the Schlenk flask in that order]2) 2mL of toluene and 0.5mL (4.8mmol) of MMA, stirring them uniformly, adding 0.024mmol of Lewis base, adding the mixture, starting the reaction, taking out the schlenk bottle from the glove box after the reaction is finished, adding a methanol solution containing 5% BHT, quenching, taking 0.2mL of the schlenk bottle in 0.4mL of deuterated chloroform, measuring the nuclear magnetism, extracting the rest liquid with a large amount of methanol, taking out the solid, drying at 40 ℃ in a vacuum drying oven to constant weight, calculating the conversion rate according to the nuclear magnetism result, and measuring the molecular weight and molecular weight distribution of the obtained polymer by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 2[ Al (mbmp) Me]2Co-catalysis of MMA polymerization with different Lewis bases
Figure BDA0002409604390000051
Through the group of experiments, the initiation efficiency of the dual-core aluminum Lewis acid and the adopted Lewis base to the MMA monomer is proved to be 100%. The superiority of binuclear aluminum Lewis acid can be obtained.
Example 3
The reaction was carried out in a glovebox and the indicated Lewis acid ([ Al (mbmp) Me) was added to the Schlenk flask in succession]2) 2mL of solvent and a defined amount of MMA, stirring them until homogeneous and adding a Lewis base (A), (B), (C)iPrIm) After the addition, the reaction was started, and after the reaction was completed, the schlenk bottle was taken out from the glove box, quenched by adding a methanol solution containing 5% BHT, 0.2mL of the solution was taken out in 0.4mL of deuterated chloroform to measure nuclear magnetism, and then the remaining liquid was extracted with a large amount of methanol, and the solid was taken out, dried in a vacuum oven at 40 ℃ to a constant weight, and the conversion rate was calculated from the nuclear magnetism result, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 3 polymerization of MMA in different solvents
Figure BDA0002409604390000052
Through the experiments of different solvents, the binuclear Lewis acid-base pair can show excellent catalytic activity in different reagents.
Example 4
The reaction was carried out in a glovebox and 0.024mmol of Lewis acid ([ Al (mbmp) Me) was added to the Schlenk flask in that order]2) 2mL of methylene chloride and 0.68mL (4.8mmol) of nBA, adding 0.024mmol of Lewis base after stirring uniformly, finishing the addition, timing the start of the reaction, taking out the Schlenk bottle from the glove box after the reaction is finished, adding a methanol solution containing 5% BHT for quenching, taking 0.2mL of the solution in 0.4mL of deuterated chloroform for detecting the nuclear magnetism, extracting the residual liquid with a large amount of methanol, taking out the solid, drying the solid in a vacuum drying oven at 40 ℃ to constant weight, calculating the conversion rate according to the nuclear magnetism result, and permeating the gelThe molecular weight and molecular weight distribution of the resulting polymer were determined by chromatography. The reaction conditions and test results were as follows:
TABLE 4[ Al (mbmp) Me]2Concerted catalysis of nBA polymerization with different Lewis bases
Figure BDA0002409604390000061
Through the group of experiments, the Lewis acid-base pair composed of the binuclear aluminum Lewis acid and the organic phosphorus has excellent catalytic activity on the nBA monomer and controllable molecular weight distribution.
Example 5
In a glove box, a specified amount of Lewis acid ([ Al (mbmp) Me) was added to a Schlenk flask]2) After adding 2mL of toluene solution and stirring well, a prescribed amount of nBA was added, and a prescribed amount of Lewis base (MesIm). After the addition, the reaction was started, after the reaction was completed, the Schlenk bottle was taken out from the glove box, quenched by adding a methanol solution containing 5% BHT, 0.2mL was taken out in 0.4mL of deuterated chloroform to measure nuclear magnetism, the remaining liquid was extracted with a large amount of methanol, the solid was taken out, dried in a vacuum oven at 40 ℃ to constant weight, the conversion was calculated from the nuclear magnetism result, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 5 treatment with basesMesIm) The polymerization results obtained as Lewis base under different reaction conditions are shown in the table below
Figure BDA0002409604390000062
Figure BDA0002409604390000071
Through the set of experiments, the binuclear aluminum-based Lewis acid and carbene are proved to be based onMesImThe composed Lewis acid-base pair has excellent performance on the nBA monomerThe molecular weight distribution is controllable, and the molecular weight of the polymer is linearly increased along with the linear increase of the monomer amount, thereby proving to be controllable polymerization.
Example 6
The reaction was carried out in a glovebox and the indicated Lewis acid ([ Al (mbmp) Me) was added to the Schlenk flask in succession]2) 2mL of solvent and a fixed amount of nBA, stirring well, and adding a Lewis base (iPrIm) After the addition, the reaction was started, and after the reaction was completed, the Schlenk bottle was taken out from the glove box, quenched by adding a methanol solution containing 5% BHT, 0.2mL was taken out in 0.4mL of deuterated chloroform to measure nuclear magnetism, and then the remaining liquid was extracted with a large amount of methanol, and the solid was taken out, dried in a vacuum oven at 40 ℃ to constant weight, and the conversion rate was calculated from the nuclear magnetism result, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 6 polymerization of nBA in different solvents
Figure BDA0002409604390000072
Through the set of experiments, the binuclear aluminum-based Lewis acid and carbene are proved to be based oniPrImThe composed Lewis acid-base pairs have excellent catalytic activity on nBA monomers in different solvents, the molecular weight distribution is controllable, and the molecular weight of the polymer is linearly increased along with the linear increase of the monomer amount, which proves that the polymerization is controllable.
Example 7
In a glove box, a quantity of Lewis acid ([ Al (mbmp) Me) was added to a Schlenk flask]2) Then 5mL of toluene solvent was added to dissolve it sufficiently, 1.5mL (mmol) of MMA was added thereto, and the prescribed amount of Lewis base (b) (after it had reacted sufficiently) was addediPrIm) After the addition, the reaction was started, 0.2mL of the monomer was completely converted and placed in a 5mL glass bottle for further use, the same amount of MMA was added, and the process was repeated three times, and after the reaction was completed, the Schlenk bottle was taken out of the glove box and quenched by adding a 5% BHT-containing methanol solution0.2mL of the polymer was taken out of a 5mL glass bottle for later use, the remaining liquid was extracted with a large amount of methanol, the solid was taken out, dried in a vacuum oven at 40 ℃ to constant weight, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 7 Experimental results for chain growth of MMA polymerization
Figure BDA0002409604390000081
The above chain extension experiments demonstrate that the above system is a living polymerization for MMA.
Example 8
In a glove box, a quantity of Lewis acid ([ Al (mbmp) Me) was added to a Schlenk flask]2) Then 5mL of dichloromethane solvent was added to dissolve it sufficiently, 0.8mL (mmol) of nBA was added thereto, and the prescribed amount of Lewis base (b) was added after it had reacted sufficientlyiPrIm) After the addition, reaction was started, 0.2mL of monomer was taken out of a 5mL glass bottle for further use after complete conversion, the same amount of nBA was added, and the process was repeated three times, after the reaction was completed, the schlenk bottle was taken out of the glove box, a methanol solution containing 5% BHT was added to quench, 0.2mL of monomer was taken out of the 5mL glass bottle for further use, the remaining liquid was extracted with a large amount of methanol, the solid was taken out, dried in a vacuum drying oven at 40 ℃ to constant weight, and the molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The reaction conditions and test results were as follows:
TABLE 8 Experimental results for chain growth of nBA polymerization
Figure BDA0002409604390000082
The above chain extension experiments demonstrated that the above system is living polymerization to nBA.

Claims (4)

1.一种基于双核铝路易斯酸的受阻路易斯酸碱对催化乙烯基单体聚合的方法，其特征在于，该方法是在有机溶剂中，室温下，以乙烯基极性单体为原料，在双核铝Lewis酸和Lewis碱组成的受阻路易斯酸碱对的催化作用下进行共轭加成聚合反应，聚合时间为1s-2h，反应结束后用甲醇淬灭；1. a method based on the hindered Lewis acid-base of dinuclear aluminium Lewis acid to catalysis vinyl monomer polymerization, it is characterized in that, the method is in organic solvent, at room temperature, with vinyl polar monomer as raw material, in Conjugate addition polymerization is carried out under the catalysis of the hindered Lewis acid-base pair composed of dinuclear aluminum Lewis acid and Lewis base, the polymerization time is 1s-2h, and the reaction is quenched with methanol; 所述的双核铝Lewis酸的结构式如下：The structural formula of described dinuclear aluminium Lewis acid is as follows:
Figure FDA0003358354010000011
Figure FDA0003358354010000011
 式中，R1为叔丁基，R2为甲基，R3为甲基；In the formula, R 1 is tert-butyl, R 2 is methyl, and R 3 is methyl; 所述的乙烯基极性单体的结构式为：The structural formula of the vinyl polar monomer is:
Figure FDA0003358354010000012
Figure FDA0003358354010000012
 式中，R1为烷基、芳基、链烯基、烷基硅烷基或链烯基硅烷基，R2为烷基、芳基、链烯基、烷基硅烷基或链烯基硅烷基；In the formula, R 1 is an alkyl group, an aryl group, an alkenyl group, an alkylsilyl group or an alkenylsilyl group, and R 2 is an alkyl group, an aryl group, an alkenyl group, an alkylsilyl group or an alkenylsilyl group ; 所述的乙烯基极性单体、双铝类Lewis酸和Lewis碱的摩尔比为(200-3200):(1-5):(1-5)；其中双铝类Lewis酸和Lewis碱的摩尔比为1:1；The molar ratio of the vinyl polar monomer, bis-aluminum Lewis acid and Lewis base is (200-3200):(1-5):(1-5); wherein the ratio of bis-aluminum Lewis acid and Lewis base is The molar ratio is 1:1; 所述的Lewis碱的结构为：The structure of the Lewis base is:
Figure FDA0003358354010000013
Figure FDA0003358354010000013
 其中，R1为环己基，乙基，苯基，4-甲氧苯基或4-甲基苯基。Wherein, R 1 is cyclohexyl, ethyl, phenyl, 4-methoxyphenyl or 4-methylphenyl. 2.根据权利要求1所述的一种基于双核铝路易斯酸的受阻路易斯酸碱对催化乙烯基单体聚合的方法，其特征在于，所述的有机溶剂为甲苯，四氢呋喃，己烷，二氯甲烷中的一种或两种以上以任意比例混合，乙烯基单体在有机溶剂中的浓度为1mol/L-10mol/L。2. a kind of method based on the hindered Lewis acid-base pair catalysis vinyl monomer polymerization of binuclear aluminium Lewis acid according to claim 1, is characterized in that, described organic solvent is toluene, tetrahydrofuran, hexane, dichloride One or more of the methanes are mixed in any proportion, and the concentration of the vinyl monomer in the organic solvent is 1 mol/L-10 mol/L. 3.根据权利要求1所述的一种基于双核铝路易斯酸的受阻路易斯酸碱对催化乙烯基单体聚合的方法，其特征在于，淬灭剂为含有BHT的甲醇溶液，含有BHT的质量分数为5％-10％。3. a kind of method for catalyzing vinyl monomer polymerization based on the hindered Lewis acid-base of binuclear aluminium Lewis acid according to claim 1, it is characterized in that, quencher is the methanol solution containing BHT, the mass fraction containing BHT 5%-10%. 4.根据权利要求1或3所述的一种基于双核铝路易斯酸的受阻路易斯酸碱对催化乙烯基单体聚合的方法，其特征在于，淬灭剂的使用量与受阻路易斯酸碱对的摩尔比为1：1。4. a kind of method based on the hindered Lewis acid-base pair of catalyzed vinyl monomer polymerization based on binuclear aluminium Lewis acid according to claim 1 and 3, it is characterized in that, the usage amount of quencher and hindered Lewis acid-base pair The molar ratio is 1:1.
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