CN111320717B - Method for catalyzing vinyl monomer polymerization by using hindered Lewis acid-base pair based on binuclear aluminum Lewis acid - Google Patents
Method for catalyzing vinyl monomer polymerization by using hindered Lewis acid-base pair based on binuclear aluminum Lewis acid Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 46
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- -1 aluminum Lewis acid Chemical class 0.000 title claims abstract description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 26
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002585 base Substances 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 150000007527 lewis bases Chemical class 0.000 claims description 23
- 239000002879 Lewis base Substances 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 21
- 238000009826 distribution Methods 0.000 abstract description 19
- 150000007517 lewis acids Chemical class 0.000 abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000005311 nuclear magnetism Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000012661 block copolymerization Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010550 living polymerization reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- 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
- 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
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- 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
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- 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
- C08F4/54—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 together with other compounds thereof
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
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
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:
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:
wherein R is methyl, ethyl, isopropyl, tert-butyl or 2,4, 6-trimethylphenyl.
More particularly, the organic phosphorus has the formula:
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:
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
Wherein R is1Is tert-butyl, R2Is methyl, R3Is methyl.
The structure and numbering of Lewis bases is as follows:
tBuIm：
MesIm：
iPrIm：
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
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
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
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
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
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
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
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
The above chain extension experiments demonstrated that the above system is living polymerization to nBA.
Claims (4)
1. A method for catalyzing vinyl monomer polymerization by a hindered Lewis acid-base pair based on binuclear aluminum Lewis acid is characterized in that the method is to perform conjugate addition polymerization reaction in an organic solvent at room temperature by taking a vinyl polar monomer as a raw material under the catalysis of the hindered Lewis acid-base pair consisting of binuclear aluminum Lewis acid and Lewis base, wherein the polymerization time is 1s-2h, and the reaction is quenched by methanol after the reaction is finished;
the structural formula of the binuclear aluminum Lewis acid is as follows:
in the formula, R1Is tert-butyl, R2Is methyl, R3Is methyl;
the structural formula of the vinyl polar monomer is as follows:
in the formula, R1Is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl, R2Is alkyl, aryl, alkenyl, alkylsilyl or alkenylsilyl;
the mol ratio of the vinyl polar monomer, the double aluminum Lewis acid and the Lewis base is (200) -3200 (1-5) to (1-5); wherein the molar ratio of the double-aluminum Lewis acid to the Lewis base is 1: 1;
the structure of the Lewis base is as follows:
wherein R is1Cyclohexyl, ethyl, phenyl, 4-methoxyphenyl or 4-methylphenyl.
2. The method according to claim 1, wherein the organic solvent is one or more of toluene, tetrahydrofuran, hexane and dichloromethane, and the concentration of the vinyl monomer in the organic solvent is 1mol/L-10 mol/L.
3. The method for catalyzing vinyl monomer polymerization by using hindered lewis acid-base pair based on binuclear aluminum lewis acid as claimed in claim 1, wherein the quenching agent is a methanol solution containing BHT with a mass fraction of 5% -10%.
4. The method for catalyzing vinyl monomer polymerization by using hindered lewis acid-base pair based on binuclear aluminum lewis acid according to claim 1 or 3, wherein the molar ratio of the usage amount of the quenching agent to the hindered lewis acid-base pair is 1: 1.
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