Application of Lewis acid-base pair in catalysis of functional monomer polymerization

Abstract

The invention belongs to the technical field of catalytic synthesis, and particularly relates to application of a Lewis acid-base pair in catalysis of functional monomer polymerization. A common polymerization method is poor in polymerization controllability on monomers containing polyalkenyl, alkynyl and conjugated dialkenyl, the molecular weight of a polymer obtained at a low monomer conversion rate is uncontrollable, the molecular weight distribution is wide, and a cross-linking phenomenon occurs at a high monomer conversion rate. By utilizing a specific Lewis acid-base pair and adjusting the electronic effect and steric hindrance effect of the Lewis acid and the Lewis base, the active controllable polymerization of the functionalized monomer can be catalyzed, the polymer containing the functionalized sites and having a clear structure is obtained, the molecular weight is controllable, the molecular weight distribution is narrow, the end group structure is controllable, and the preparation method is simple and convenient. The position and density of the functionalized site are convenient to adjust, an efficient platform is provided for post-modification preparation of the functional polymer material, and the functional polymer material is prepared by combining with a click reaction.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic synthesis, and in particular relates to application of a Lewis acid-base pair in catalyzing the polymerization of functionalized monomers. Background Art

[0002] Functional polymer materials are widely used in various fields due to their specific physical and chemical functions, such as photosensitive polymers, conductive polymers, photoelectric conversion polymers, medical polymers and polymer catalysts. However, the synthesis of functional polymer materials is difficult, and there are two main methods. One method is to prepare functional polymer materials by polymerizing monomers with specific groups.

[0003] Another method is to first obtain a functionalized polymer precursor through polymerization, and then transform the functionalized sites through certain chemical reactions to introduce specific groups to prepare functional polymer materials. However, this method currently cannot guarantee that the polymer precursor contains the target functionalized sites. Summary of the invention

[0004] The purpose of the present invention is to provide an application of a Lewis acid-base pair in catalyzing the polymerization of functionalized monomers. The present invention catalyzes the active and controllable polymerization of functionalized monomers through a specific Lewis acid-base pair to obtain a polymer with a clear structure and containing functionalized sites.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides an application of a Lewis acid-base pair in catalyzing the polymerization of a functionalized monomer, wherein the Lewis acid-base pair comprises a Lewis acid and a Lewis base; the Lewis base comprises one or more of a Lewis base of formula NHO, a Lewis base of formula IAP, a Lewis base of formula DIAP and a Lewis base of formula PyAP;

[0007]

[0008] In the formula NHO, formula IAP, formula DIAP and formula PyAP, n=1 to 9, R 1 is hydrogen, alkyl or phenyl; R 2 is hydrogen, alkyl, phenyl or substituted phenyl; R 3 is alkyl, phenyl or substituted phenyl; R 4 is alkyl, phenyl or substituted phenyl; R 5 is hydrogen, alkyl, phenyl or substituted phenyl; R 6 It is hydrogen, alkyl, phenyl or substituted phenyl.

[0009] Preferably, the application comprises the following steps: mixing a monomer, a Lewis acid-base pair and an organic solvent to carry out a polymerization reaction to obtain a polymer.

[0010] Preferably, the molar ratio of the monomer to the Lewis base in the Lewis acid-base pair is 15 to 50,000:1.

[0011] Preferably, the concentration of the monomer in the mixed solution is not less than 0.2M.

[0012] Preferably, the polymerization reaction temperature is -50 to 100°C, and the insulation reaction time is 10s to 72h.

[0013] Preferably, the monomer includes one or more of butyl methacrylate, propargyl methacrylate and methacrylate.

[0014] Preferably, the organic solvent includes one or more of benzene homologues, furan compounds, amide compounds and substituted benzenes.

[0015] Preferably, the monomer, Lewis acid-base pair and organic solvent are mixed as follows: the monomer and the first part of the organic solvent are mixed to obtain a monomer solution, the Lewis acid and the second part of the organic solvent are mixed to obtain a Lewis acid solution, the Lewis base and the third part of the organic solvent are mixed to obtain a Lewis base solution, the monomer solution, the Lewis acid solution and the remaining part of the organic solvent are mixed to obtain a premixed solution, and then the premixed solution and the Lewis base solution are mixed.

[0016] Preferably, the molar ratio of the Lewis acid to the Lewis base is not less than 2:1.

[0017] Preferably, the Lewis acid comprises one or more of the Lewis acid of formula A-1, the Lewis acid of formula A-2, the Lewis acid of formula A-3 and the Lewis acid of formula A-4;

[0018]

[0019] In Formula A-1 to Formula A-4, R 1 is alkyl or halogen; R 2 is hydrogen, alkyl, substituted alkyl or halogen; R 3 is hydrogen, alkyl or halogen.

[0020] The present invention provides an application of a Lewis acid-base pair in catalyzing the polymerization of functional monomers. Due to the poisoning effect of functional groups such as alkenyl, alkynyl and conjugated diene groups on catalysts, or the occurrence of multiple side reactions of functional groups during the polymerization process, the commonly used catalysts have poor controllability over the polymerization of monomers containing polyalkenyl, alkynyl and conjugated diene groups, and multiple side reactions (including the coordination effect of alkenyl or alkynyl on catalysts, chain transfer or crosslinking caused by free radicals generated on alkenyl or alkynyl groups, etc.) may occur during the polymerization reaction, and the reaction conditions need to be strictly controlled or the polymerization reaction needs to be quenched in time to avoid crosslinking. At the same time, the molecular weight of the obtained polymer is uncontrollable, the molecular weight distribution is wide, and crosslinking occurs at a high monomer conversion rate. The present invention adopts a specific Lewis acid-base pair, and by adjusting the electronic effect and steric hindrance effect of the Lewis acid and the Lewis base, it can catalyze the active controllable polymerization of functionalized monomers to obtain a polymer with a clear structure and containing functionalized sites, and the molecular weight is controllable, the molecular weight distribution is narrow, the end group structure is controllable, and the position and density of the functionalized sites (such as alkynyl, alkenyl, and conjugated diene groups) are conveniently adjusted, thereby overcoming the problem that it is difficult to synthesize functionalized polymers with precise structures, and introducing functionalized sites with high reaction activity, thereby overcoming the problem that the functionalized sites are difficult to quickly and completely convert into specific groups due to the large steric hindrance of the polymer, providing an efficient platform for post-modification preparation of functional polymer materials, and combining with click reaction to prepare functional polymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0022] Figure 1 Different from Examples 3 and 7 to 13 [AMA] 0 / [IAP-1] 0 GPC curves of polymers prepared in the ratio;

[0023] Figure 2 is a graph showing the relationship between monomer conversion and the molecular weight and molecular weight distribution of the prepared polymer;

[0024] Figure 3 IAP-1 / i Bu 2 MALDI TOF spectrum of low molecular weight PAMA produced by the polymerization of AMA catalyzed by Al(BHT);

[0025] Figure 4 IAP-1 / i Bu 2Overlay of GPC curves of AMA chain extension catalyzed by Al(BHT) (a) and IAP-1 / i Bu 2 Overlay of GPC curves of MMA and AMA block copolymerization catalyzed by Al(BHT) (b);

[0026] Figure 5 This is the H-NMR spectrum of the thiol-olefin addition click reaction of the olefin-containing polymer with mercaptoethanol;

[0027] Figure 6 Different from Examples 15 to 19 [ByMA] 0 / [IAP-1] 0 GPC curves of polymers prepared in the ratio;

[0028] Figure 7 is a graph showing the relationship between monomer conversion and the molecular weight and molecular weight distribution of the prepared polymer;

[0029] Figure 8 IAP-1 / i Bu 2 MALDI TOF spectrum of low molecular weight PByMA produced by Al(BHT)-catalyzed ByMA polymerization;

[0030] Fig. 9 IAP-1 / i Bu 2 Overlay of GPC curves of ByMA chain extension catalyzed by Al(BHT) (a) and IAP-1 / i Bu 2 Overlay of GPC curves of block copolymerization of ByMA, MMA and AMA catalyzed by Al(BHT) (b);

[0031] Fig.10 H NMR spectrum of in situ CuAAC reaction of small molecules containing alkenyl, alkynyl and azide groups;

[0032] Fig.11 Overlay of H NMR spectra of in situ CuAAC reaction of small molecules containing alkenyl, alkynyl and azide groups (top) and thiol-olefin reaction with in situ addition of thiol (bottom);

[0033] Fig.12 The CuAAC reaction of ethyl azidoacetate (upper) and H NMR spectra of alkenyl- and alkynyl-containing polymers (lower) is shown;

[0034] Fig.13 This is an overlay diagram of the tensile curves of the self-healing material prepared by alkenyl and alkyne-containing polymers before and after repair at 50°C and 5h;

[0035] Fig.14 Different from Examples 30 to 32 [HDEMA]0 / [IAP-1] 0 GPC curves of polymers prepared with different Lewis acids;

[0036] Fig.15 It is the superposition of H NMR spectra of the polymer containing conjugated diene group (upper), triazolinedione (lower) and the addition reaction of the polymer containing conjugated diene group and triazolinedione (middle);

[0037] Fig.16 The superposition of H NMR spectra of the reaction of a polymer containing a conjugated diene group with a triazolinedione (top), the reaction of a polymer containing an alkynyl group with an azide compound (middle), and a polymer containing a conjugated diene group and an alkynyl group undergoing a continuous click reaction (bottom);

[0038] Fig.17 The diagram is a mechanism diagram of preparing polymers by using Lewis acid-base pairs to catalyze the polymerization of monomers. DETAILED DESCRIPTION

[0039] The present invention provides an application of a Lewis acid-base pair in catalyzing the polymerization of a functionalized monomer, wherein the Lewis acid-base pair comprises a Lewis acid and a Lewis base; the Lewis base comprises one or more of a Lewis base of formula NHO, a Lewis base of formula IAP, a Lewis base of formula DIAP and a Lewis base of formula PyAP;

[0040]

[0041] In the formula NHO, formula IAP, formula DIAP and formula PyAP, n=1 to 9, R 1 is hydrogen, alkyl or phenyl; R 2 is hydrogen, alkyl, phenyl or substituted phenyl; R 3 is alkyl, phenyl or substituted phenyl; R 4 is alkyl, phenyl or substituted phenyl; R 5 is hydrogen, alkyl, phenyl or substituted phenyl; R 6 It is hydrogen, alkyl, phenyl or substituted phenyl.

[0042] In the present invention, the application preferably comprises the following steps: mixing a monomer, a Lewis acid-base pair and an organic solvent to carry out a polymerization reaction to obtain a polymer.

[0043] The present invention mixes monomers, Lewis acid-base pairs and organic solvents to obtain a mixed solution. In the present invention, the monomers preferably include one or more of polyene-containing acrylate monomers, polyene-containing acrylamide monomers, alkynyl-containing acrylate monomers, alkynyl-containing acrylamide monomers, conjugated diene-containing acrylate monomers and conjugated diene-containing acrylamide monomers.

[0044] In the present invention, the polyolefin-containing acrylate monomer preferably includes one or more of the following: monomer of formula 1, monomer of formula 2, monomer of formula 3, monomer of formula 4, monomer of formula 5, monomer of formula 6, monomer of formula 7, monomer of formula 8, monomer of formula 9, monomer of formula 10, monomer of formula 11, monomer of formula 12, monomer of formula 13, monomer of formula 14, monomer of formula 15, monomer of formula 16, monomer of formula 17, monomer of formula 18, monomer of formula 19, monomer of formula 20, monomer of formula 21, monomer of formula 22, monomer of formula 23, monomer of formula 24, monomer of formula 25, monomer of formula 26, monomer of formula 27, monomer of formula 28, monomer of formula 29, monomer of formula 30, monomer of formula 31, monomer of formula 32, monomer of formula 33, monomer of formula 34, monomer of formula 35 and monomer of formula 36:

[0045]

[0046] In formula 1 to formula 36, ​​R 1 -H or -CH 3 , R 2 -CH 3 or -CH 2 CH 3 , R 3 It is -H or C1~C10 alkyl.

[0047] In the present invention, in Formulas 1 to 36, the C1 to C10 alkyl groups preferably include -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0048] In the present invention, the polyene-containing acrylamide monomer preferably includes one or more of the monomers of formula 37, 38, 39 or 40:

[0049]

[0050] In formula 37 to formula 40, R 1 -H or -CH3 , R 3 It is -H or C1~C10 alkyl.

[0051] In the present invention, in Formula 37 to Formula 40, the C1 to C10 alkyl group preferably includes -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0052] In the present invention, the alkynyl-containing acrylic ester monomer preferably includes one or more of the following: monomer of formula 41, monomer of formula 42, monomer of formula 43, monomer of formula 44, monomer of formula 45, monomer of formula 46, monomer of formula 47, monomer of formula 48, monomer of formula 49, monomer of formula 50, monomer of formula 51, monomer of formula 52, monomer of formula 53, monomer of formula 54, monomer of formula 55, monomer of formula 56, monomer of formula 57, monomer of formula 58, monomer of formula 59, monomer of formula 60, monomer of formula 61 and monomer of formula 62:

[0053]

[0054] In formulas 41 to 62, R 1 -H or -CH 3 , R 2 -CH 3 or -CH 2 CH 3 , R 3 It is -H or C1~C10 alkyl.

[0055] In the present invention, in Formula 41 to Formula 62, the C1 to C10 alkyl group preferably includes -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0056] In the present invention, the alkynyl-containing acrylamide monomer preferably includes one or more of the monomers of formula 63 and formula 64:

[0057]

[0058] In formula 63 and formula 64, R 1 -H or -CH 3 , R 3 It is -H or C1~C10 alkyl.

[0059] In the present invention, in Formula 63 to Formula 64, the C1 to C10 alkyl group preferably includes -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0060] In the present invention, the conjugated diene group-containing acrylate monomer preferably includes one or more of the following: monomer of formula 65, monomer of formula 66, monomer of formula 67, monomer of formula 68, monomer of formula 69, monomer of formula 70, monomer of formula 71, monomer of formula 72, monomer of formula 73, monomer of formula 74, monomer of formula 75, monomer of formula 76, monomer of formula 77, monomer of formula 78, monomer of formula 79, monomer of formula 80, monomer of formula 81, monomer of formula 82, monomer of formula 83 and monomer of formula 84:

[0061]

[0062] In formula 65 to formula 84, R 1 -H or -CH 3 , R 2 -CH 3 or -CH 2 CH 3 , R 3 It is -H or C1~C10 alkyl.

[0063] In the present invention, in Formula 65 to Formula 84, the C1 to C10 alkyl group preferably includes -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH 2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0064] In the present invention, the conjugated diene group-containing acrylamide monomer preferably includes one or more of the monomers of formula 85 and formula 86:

[0065]

[0066] In formula 85 to formula 86, R 1 -H or -CH 3 , R 3 It is -H or C1~C10 alkyl.

[0067] In the present invention, in Formula 85 to Formula 86, the C1 to C10 alkyl group preferably includes -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-CH2 CH(CH 3 )CH 3 、-CH(CH 3 )CH 2 CH 3 or -C(CH 3 ) 3 .

[0068] In a specific embodiment of the present invention, the monomer preferably includes one or more of butyl methacrylate, propargyl methacrylate and methacrylate;

[0069]

[0070] In the present invention, the molar ratio of the monomer to the Lewis base in the Lewis acid-base pair is preferably 15 to 50,000:1, and specifically can be 15:1, 50:1, 100:1, 200:1, 500:1, 1000:1, 2000:1, 10000:3, 10000:1, 15000:1, 20000:1, 30000:1, 40000:1 or 50000:1.

[0071] In the present invention, the Lewis acid-base pair is preferably added in the form of a Lewis acid solution and a Lewis base solution, respectively.

[0072] In the present invention, the organic solvent preferably includes one or more of benzene homologues, furan compounds, amide compounds and substituted benzenes, and is more preferably benzene homologues; the benzene homologues are preferably toluene; the furan compounds are preferably tetrahydrofuran; the amide compounds are preferably N,N-dimethylformamide; the substituted benzenes preferably include one or both of fluorobenzene and chlorobenzene.

[0073] In the present invention, the concentration of the monomer in the mixed solution is preferably not less than 0.2M, and specifically may be 0.2M, 0.5M, 0.94M, 1M, 2M or 4M.

[0074] In the present invention, the monomer, Lewis acid-base pair and organic solvent are preferably mixed as follows: the monomer and the first part of the organic solvent are mixed to obtain a monomer solution, the Lewis acid and the second part of the organic solvent are mixed to obtain a Lewis acid solution, the Lewis base and the third part of the organic solvent are mixed to obtain a Lewis base solution, the monomer solution, the Lewis acid solution and the remaining part of the organic solvent are mixed to obtain a premixed solution, and then the premixed solution and the Lewis base solution are mixed. The present invention controls the order and steps of adding materials, uses a small amount of catalyst, has a fast polymerization speed, does not require harsh conditions, has no cross-linking during the polymerization process, and accurately synthesizes polymers containing functionalized sites with controllable sequence and structural composition, such as random or block copolymers, especially non-cross-linked acetylenic polymers.

[0075] After obtaining the mixed solution, the present invention performs a polymerization reaction on the obtained mixed solution to obtain a polymer. In the present invention, the polymerization reaction temperature is preferably -50 to 100°C, specifically -50°C, -30°C, -10°C, 0°C, 15°C, 25°C, 45°C, 65°C, 85°C or 100°C, and the insulation reaction time is preferably 10s to 72h, specifically 10s, 30s, 1min, 10min, 30min, 1h, 10h, 30h, 50h or 72h.

[0076] The mechanism of the Lewis acid-base pair catalyzing the polymerization of monomers of the present invention is as follows Fig. 9 As shown: first, the chain is initiated: the Lewis base nucleophilically attacks the monomer activated by the Lewis acid to form a zwitterionic active species; then the chain is extended: the active chain end nucleophilically attacks the monomer activated by the Lewis acid, and the attacked site is the double bond conjugated with the carbonyl group.

[0077] In the specific Lewis acid-base pair used in the present invention, the Lewis acid preferably includes one or more of the Lewis acid of formula A-1, the Lewis acid of formula A-2, the Lewis acid of formula A-3 and the Lewis acid of formula A-4.

[0078]

[0079] In Formula A-1 to Formula A-4, R 1 is alkyl or halogen; R 2 is hydrogen, alkyl, substituted alkyl or halogen; R 3 is hydrogen, alkyl or halogen.

[0080] In the present invention, R in Formula A-1 to Formula A-4 1 , the alkyl group is preferably a C1-C10 alkyl group; the C1-C10 alkyl group is preferably a C1-C10 straight-chain alkyl group or a C1-C10 branched-chain alkyl group; the C1-C10 straight-chain alkyl group preferably includes a methyl group or an ethyl group; the C1-C10 branched-chain alkyl group preferably includes an isopropyl group or an isobutyl group; the halogen group preferably includes fluorine, chlorine or bromine.

[0081] In the present invention, R in Formula A-1 to Formula A-4 2 , the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group or an ethyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted alkyl group is preferably a polysubstituted C1~C10 alkyl group; the polysubstituted C1~C10 alkyl group is preferably a trifluoromethyl group; the halogen preferably includes fluorine, chlorine or bromine.

[0082] In the present invention, R in Formula A-1 to Formula A-43 , the alkyl group is preferably a C1-C10 alkyl group; the C1-C10 alkyl group is preferably a C1-C10 straight-chain alkyl group; the C1-C10 straight-chain alkyl group preferably includes a methyl group or an ethyl group; the halogen group preferably includes fluorine, chlorine or bromine.

[0083] In the present invention, the Lewis acid preferably includes bis(2,6-di-tert-butyl-4-methylphenoxy)methylaluminum (MeAl(BHT) 2 ), tris(pentafluorophenyl)aluminum (Al(C 6 F 5 ) 3 )、(2,6-di-tert-butyl-4-methylphenoxy)diisobutylaluminum( i Bu 2 Al(BHT)), bis(2,6-di-tert-butyl-4-methylphenoxy)isobutylaluminum( i BuAl(BHT) 2 ) and trimethylaluminum (AlMe 3 ) one or more of the following.

[0084] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 1 , the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group.

[0085] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 2 , the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted phenyl group preferably includes an alkylphenyl group or a halogenated phenyl group; the alkylphenyl group is preferably a polyalkylphenyl group; the polyalkylphenyl group preferably includes a 2,6-diisopropylphenyl group or a 1,3,5-trimethylphenyl group; the halogenated phenyl group is preferably a fluorophenyl group; the fluorophenyl group is preferably a pentafluorophenyl group.

[0086] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 3, the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted phenyl group preferably includes an alkylphenyl group or a halogenated phenyl group; the alkylphenyl group is preferably a polyalkylphenyl group; the polyalkylphenyl group preferably includes a 2,6-diisopropylphenyl group or a 1,3,5-trimethylphenyl group; the halogenated phenyl group is preferably a fluorophenyl group; the fluorophenyl group is preferably a pentafluorophenyl group.

[0087] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 4 , the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted phenyl group preferably includes an alkylphenyl group or a halogenated phenyl group; the alkylphenyl group is preferably a polyalkylphenyl group; the polyalkylphenyl group preferably includes a 2,6-diisopropylphenyl group or a 1,3,5-trimethylphenyl group; the halogenated phenyl group is preferably a fluorophenyl group; the fluorophenyl group is preferably a pentafluorophenyl group.

[0088] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 5 , the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted phenyl group preferably includes an alkylphenyl group or a halogenated phenyl group; the alkylphenyl group is preferably a polyalkylphenyl group; the polyalkylphenyl group preferably includes a 2,6-diisopropylphenyl group or a 1,3,5-trimethylphenyl group; the halogenated phenyl group is preferably a fluorophenyl group; the fluorophenyl group is preferably a pentafluorophenyl group.

[0089] In the present invention, R in the formula NHO, the formula IAP, the formula DIAP and the formula PyAP 6, the alkyl group is preferably a C1~C10 alkyl group; the C1~C10 alkyl group is preferably a C1~C10 straight-chain alkyl group or a C1~C10 branched-chain alkyl group; the C1~C10 straight-chain alkyl group preferably includes a methyl group, an ethyl group, a n-propyl group or a n-butyl group; the C1~C10 branched-chain alkyl group preferably includes an isopropyl group, an isobutyl group or a tert-butyl group; the substituted phenyl group preferably includes an alkylphenyl group or a halogenated phenyl group; the alkylphenyl group is preferably a polyalkylphenyl group; the polyalkylphenyl group preferably includes a 2,6-diisopropylphenyl group or a 1,3,5-trimethylphenyl group; the halogenated phenyl group is preferably a fluorophenyl group; the fluorophenyl group is preferably a pentafluorophenyl group.

[0090] In the present invention, the Lewis base preferably includes one or more of nitrogen heterocyclic olefin-1 (NHO-1, structure such as formula NHO-1) and guanidinophosphonium base-1 (IAP-1, structure such as formula IAP-1);

[0091]

[0092] In the present invention, the molar ratio of the Lewis acid to the Lewis base is preferably not less than 2: 1, and specifically can be 20: 1, 16: 1, 8: 1, 4: 1, 3: 1 or 2: 1. In the present invention, through the above-mentioned amounts of Lewis acid and Lewis base, one equivalent of Lewis base attacks the activated monomer to form zwitterionic active species, one equivalent of Lewis acid stabilizes the polymer chain end, and the remaining (at least one equivalent) Lewis acid activates the monomer. The larger the amount of Lewis acid used, the faster the polymerization reaction rate.

[0093] In the present invention, the method for preparing the Lewis acid-base pair preferably comprises the following steps: mixing a Lewis acid and a Lewis base to obtain the Lewis acid-base pair.

[0094] In the present invention, the Lewis acid and the Lewis base are preferably mixed by stirring.

[0095] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0096] Examples 1 to 13

[0097] The Lewis acid-base pairs used in Examples 1 to 13 are different IAP Lewis bases (denoted as LB) combined with different Lewis acids (denoted as LA); Examples 1 to 13 catalyze the polymerization of allyl methacrylate (AMA, denoted as M), comprising the following steps:

[0098]

[0099] 296 mg (2.35 mmol) of AMA was dissolved in 500 μL of toluene to obtain a monomer solution; then the toluene solution of LA was added to the monomer solution, and toluene was added after stirring for 1 minute to ensure that the concentration of the monomer in the reaction system was 0.94 M to obtain a premixed solution, and the toluene solution of LB was added to the premixed solution to obtain a mixed solution, the total volume of the mixed solution was 2.5 mL, and then a polymerization reaction was carried out at room temperature to obtain a polymer. The molar ratio of M, LA and LB, and the polymerization reaction time are shown in Table 1.

[0100] The monomer conversion rate was tested by nuclear magnetic resonance spectroscopy, and the M w and D, the results are shown in Table 1, where the calculation method of initiation efficiency (I*) is as follows:

[0101] I*=M n (Theoretical) / M n (actual);

[0102] M n (theoretical) = [MW (AMA)] × ([AMA] 0 / [IAP] 0 )×monomer conversion rate+MW(end group).

[0103] Table 1 Test results of Examples 1 to 13

[0104]

[0105]

[0106] According to Table 1, the three Lewis acids (Al(C 6 F 5 ) 3、 MeAl(BHT) 2、 i Bu 2 Al(BHT)) combined with four Lewis bases (IAP-1, IAP-2, IAP-3, and IAP-4) all have high polymerization activity, and all polymerization reactions can reach a monomer conversion rate close to 100% in a relatively short period of time without crosslinking; as the monomer ratio increases, the molecular weight of the resulting polymer increases linearly and maintains a narrow distribution, with an initiation efficiency close to 100%.

[0107] Embodiments 14 to 19

[0108] The Lewis acid-base pair used in Examples 14-19 is IAP-1 compound (denoted as LB) combined with i Bu 2Al(BHT) (denoted as LA); Examples 14 to 19 catalyze the polymerization of butyl methacrylate (ByMA, denoted as M), comprising the following steps:

[0109] 324 mg (2.35 mmol) of ByMA was dissolved in 500 μL of toluene to obtain a monomer solution; then, the monomer solution was added i Bu 2 The toluene solution of Al(BHT) was stirred for 1 minute and then toluene was added to ensure that the concentration of the monomer in the reaction system was 0.94M to obtain a premixed solution. The toluene solution of the compound of formula IAP-1 was added to the premixed solution to obtain a mixed solution. The total volume of the mixed solution was 2.5 mL, and then a polymerization reaction was carried out at room temperature to obtain a polymer. The molar ratio of M, LA and LB and the polymerization reaction time are shown in Table 2.

[0110] The monomer conversion rate was tested by nuclear magnetic resonance spectroscopy, and the M w and The results are shown in Table 2, where the calculation method of initiation efficiency (I*) is as follows:

[0111] I*=M n (Theoretical) / M n (actual);

[0112] M n (theoretical) = [MW (ByMA)] × ([ByMA] 0 / [IAP-1] 0 )×monomer conversion rate+MW(end group).

[0113] Table 2 Test results of Examples 14 to 19

[0114]

[0115] It can be seen from Table 2 that all polymerization reactions can reach 100% monomer conversion in a relatively short time and the polymerization is completed; as the monomer ratio increases, the molecular weight of the resulting polymer increases linearly and maintains a narrow distribution, with an initiation efficiency close to 100%.

[0116] Embodiments 20 to 24

[0117] Examples 20 to 24 utilize a compound of formula NHO-1 (denoted as LB) in combination with different Lewis acids (denoted as LA) to catalyze the polymerization of butyl methacrylate (ByMA) (denoted as M), comprising the following steps:

[0118] 324 mg (2.35 mmol) of ByMA was dissolved in 500 μL of toluene to obtain a monomer solution; then a toluene solution of Lewis acid was added to the monomer solution, and toluene was added after stirring for 1 minute to ensure that the concentration of the monomer in the reaction system was 0.94 M to obtain a premixed solution, and then a toluene solution of a compound of formula NHO-1 was added to the premixed solution to obtain a mixed solution with a total volume of 2.5 mL. Then, a polymerization reaction was carried out at room temperature to obtain a polymer. The molar ratio of M, LA and LB and the polymerization reaction time are shown in Table 3. The test method is the same as above, and the results are shown in Table 3.

[0119] Table 3 Test results of Examples 20 to 24

[0120]

[0121] According to Table 3, it can be seen that the polymerization of ByMA can be achieved by combining NHO-1 as LB with different LAs; 6 F 5 ) 3 ) or moderately acidic and sterically hindered (MeAl(BHT) 2 , i Bu 2 Al(BHT)) can achieve complete conversion of monomers, and obtain polymers with molecular weights close to the expected molecular weight and narrow molecular weight distribution, moderate acidity but large steric hindrance ( i BuAl(BHT) 2 ) or weakly acidic (AlMe 3 ) showed a slow polymerization rate.

[0122] Embodiments 25 to 29

[0123] Examples 25 to 29 utilize the compound of formula IAP-1 in combination with different Lewis acids to catalyze the polymerization of butyl methacrylate (ByMA), comprising the following steps:

[0124] 324 mg (2.35 mmol) of ByMA was dissolved in 500 μL of toluene to obtain a monomer solution; then a toluene solution of Lewis acid was added to the monomer solution, and toluene was added after stirring for 1 minute to ensure that the concentration of the monomer in the reaction system was 0.94 M to obtain a premixed solution, and a toluene solution of the compound of formula IAP-1 was added to the premixed solution to obtain a mixed solution, the total volume of the mixed solution was 2.5 mL, and then a polymerization reaction was carried out at room temperature to obtain a polymer. The molar ratio of M, LA and LB and the polymerization reaction time are shown in Table 4. The test method is the same as above, and the results are shown in Table 4.

[0125] Table 4 Test results of Examples 25 to 29

[0126]

[0127]

[0128] According to Table 4, IAP-1 as LB can be used to combine with different LAs to achieve the polymerization of ByMA; among them, moderate acidity and moderate steric hindrance ( i Bu 2 Al(BHT)) can achieve complete conversion of monomers to obtain polymers with expected molecular weight and narrow molecular weight distribution, with high acidity (Al(C 6 F 5 ) 3 ) or moderately acidic and moderately hindered (MeAl(BHT) 2 ) LA can achieve complete conversion of monomers, but the molecular weight obtained is lower than the theoretical molecular weight, and the acidity is moderate but the steric hindrance is large ( i BuAl(BHT) 2 ) or weakly acidic (AlMe 3 ) showed a slow polymerization rate.

[0129] Embodiments 30 to 32

[0130] Examples 30 to 32 utilize the compound of formula IAP-1 in combination with different Lewis acids to catalyze the polymerization of (2,4-hexadiene) methacrylate (HDEMA), comprising the following steps:

[0131]

[0132] 390 mg (2.35 mmol) of HDEMA was dissolved in 500 μL of toluene to obtain a monomer solution; then a toluene solution of Lewis acid was added to the monomer solution, and toluene was added after stirring for 1 minute to ensure that the concentration of the monomer in the reaction system was 0.94 M to obtain a premixed solution, and a toluene solution of the compound of formula IAP-1 was added to the premixed solution to obtain a mixed solution, the total volume of the mixed solution was 2.5 mL, and then a polymerization reaction was carried out at room temperature to obtain a polymer. The molar ratio of M, LA and LB and the polymerization reaction time are shown in Table 5. The test method is the same as above, and the results are shown in Table 5.

[0133] The monomer conversion rate was tested by nuclear magnetic resonance spectroscopy, and the M n and The results are shown in Table 5, where the calculation method of the initiation efficiency (I*) is as follows:

[0134] I*=M n (Theoretical) / M n (actual);

[0135] M n (Theoretical)=[MW(HDEMA)]×([HDEMA]0 / [IAP-1] 0 )×monomer conversion+MW(end group).

[0136] Table 5 Test results of Examples 30 to 32

[0137]

[0138] According to Table 5, IAP-1 was used as LB and combined with different LAs ( i Bu 2 Al(BHT), MeAl(BHT) 2 ) has high polymerization activity and can achieve complete conversion of HDEMA in a short time.

[0139] Test Example 1

[0140] Different from Examples 3, 7 to 13 [AMA] 0 / [IAP-1] 0 The polymer prepared in the ratio was subjected to GPC analysis, and the results were as follows Figure 1 As shown. Figure 1 It can be seen that with the [AMA] 0 / [IAP-1] 0 As the ratio increases, the molecular weight of the prepared polymer gradually increases, proving that the present invention can control [AMA] 0 / [IAP-1] 0 The amount used is to obtain a polymer with the desired molecular weight.

[0141] Test Example 2

[0142] The relationship between the monomer conversion rate and the molecular weight and molecular weight distribution of the prepared polymer was tested. Referring to Example 9, the amount of raw materials used was [AMA] 0 / [IAP-1] 0 =1600:1, the result is Figure 2 As shown, MALDI TOF test was performed on the polymerization of AMA to produce low molecular weight PAMA. The results are shown in Figure 3 shown.

[0143] according to Figures 2-3 It can be seen that the molecular weight of the polymer increases linearly with the polymerization reaction and maintains a narrow distribution. There is no backbiting at the end of the polymer chain, indicating that IAP-1 / i Bu 2 Al(BHT)-catalyzed AMA polymerization has the characteristics of living polymerization.

[0144] Test Example 3

[0145] IAP-1 / i Bu2 GPC curve superposition analysis of Al(BHT) catalyzed AMA chain extension and catalyzed MMA and AMA block copolymerization, IAP-1 / i Bu 2 Al(BHT) can catalyze multiple chain extensions of AMA monomers or multiple block copolymerizations with other methacrylate monomers. The specific test method is as follows: 296 mg (2.35 mmol) of AMA is dissolved in 500 μL of toluene, and then i Bu 2 A toluene solution of Al(BHT) was stirred for 1 minute, and then toluene was added. The toluene solution of the compound of formula IAP-1 was added thereto to obtain a mixed solution with a total volume of 2.5 mL. After the monomers were completely converted, the same amount of AMA or methyl methacrylate (MMA) (2.35 mmol) was added. This was repeated several times. After all monomers were completely converted, the reaction bottle was taken out of the glove box, and a 5% HCl / methanol solution was added to terminate the polymerization reaction. The polymer was filtered out, washed thoroughly with methanol, and dried at 50° C. in a vacuum oven to a constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The results are as follows: Figure 4 shown.

[0146] according to Figure 4 It can be seen that the polymerization reaction can achieve further growth of the polymer chain by continuous addition without quenching, which once again verifies the IAP-1 / i Bu 2 Al(BHT)-catalyzed AMA polymerization has the characteristics of living polymerization.

[0147] Test Example 4

[0148] Combined with the thiol-olefin addition click reaction, polymers containing olefin groups can be used as an efficient platform for post-modification preparation of functional polymer materials. The thiol-olefin addition reaction of poly(allyl methacrylate) (PAMA) and mercaptoethanol was analyzed by H NMR spectroscopy. All olefin groups in the polymer were converted into hydroxyl groups. Figure 5 shown.

[0149] according to Figure 5 It can be seen that the olefin groups contained in the polymer can be quantitatively converted into specific functional groups. Therefore, olefin-containing polymers can be regarded as transformation platforms. Through efficient post-modification reactions, different structural groups can be introduced to give the polymer materials a variety of properties.

[0150] Test Example 5

[0151] Different from Examples 15 to 19 [ByMA] 0 / [IAP-1] 0 The polymer prepared in the ratio was subjected to GPC analysis, and the results were as follows Figure 6 As shown. Figure 6 It can be seen that with [ByMA] 0 / [IAP-1] 0 As the ratio increases, the molecular weight of the prepared polymer gradually increases, proving that the present invention can control [ByMA] 0 / [IAP-1] 0 The amount used is to obtain a polymer with the desired molecular weight.

[0152] Test Example 6

[0153] The relationship between the monomer conversion rate and the molecular weight and molecular weight distribution of the prepared polymer was tested. Referring to Example 17, the amount of raw materials used was [ByMA] 0 / [IAP-1] 0 =800:1, the result is as follows Figure 7 As shown, the MALDI TOF test of ByMA polymerization to produce low molecular weight PByMA was performed, and the results are shown Figure 8 shown.

[0154] according to Figures 7-8 It can be seen that the molecular weight of the polymer increases linearly with the polymerization reaction and maintains a narrow distribution. There is no backbiting at the end of the polymer chain, indicating that IAP-1 / i Bu 2 Al(BHT)-catalyzed ByMA polymerization has the characteristics of living polymerization.

[0155] Test Example 7

[0156] IAP-1 / i Bu 2 Al(BHT) catalyzed ByMA chain extension and catalyzed ByMA, MMA, AMA block copolymerization for GPC curve superposition analysis, IAP-1 / i Bu 2 Al(BHT) can catalyze multiple chain extensions of ByMA monomers or multiple block copolymerizations with other methacrylate monomers. The specific test method is as follows: 324 mg (2.35 mmol) of ByMA is dissolved in 500 μL of toluene, and then i Bu 2A toluene solution of Al(BHT) was stirred for 1 minute, and then toluene was added. The toluene solution of the compound of formula IAP-1 was added thereto to obtain a mixed solution with a total volume of 2.5 mL. After the monomers were completely converted, the same amount of ByMA or allyl methacrylate (AMA) or methyl methacrylate (MMA) (2.35 mmol) was added. This was repeated several times. After all monomers were completely converted, the reaction bottle was taken out of the glove box, and a 5% HCl / methanol solution was added to terminate the polymerization reaction. The polymer was filtered out, washed thoroughly with methanol, and dried at 50° C. in vacuum to constant weight. The molecular weight and molecular weight distribution of the obtained polymer were measured by gel permeation chromatography. The results are as follows: Fig. 9 shown.

[0157] according to Fig. 9 It can be seen that the polymerization reaction can achieve further growth of the polymer chain by continuous addition without quenching, which once again verifies the IAP-1 / i Bu 2 Al(BHT)-catalyzed ByMA polymerization has the characteristics of living polymerization.

[0158] Test Case 8

[0159] Combined with click reactions or other efficient organic reactions, polymers containing alkyne and alkene groups can be used as an efficient platform for post-modification preparation of functional polymer materials. The in situ Cu(I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC reaction) of small molecules containing alkenyl, alkynyl and azide groups was analyzed by nuclear magnetic resonance hydrogen spectrum. The results are as follows Fig.10 The results are shown in Figure 2. The in situ CuAAC reaction of small molecules containing alkenyl, alkynyl and azide groups (above) and the in situ addition of thiol for thiol-olefin reaction (below) were analyzed by NMR hydrogen spectrum superposition. Fig.11 shown.

[0160] according to Figures 10-11 It can be seen that the alkynyl and alkenyl groups existing simultaneously in the system can be transformed separately through sequential reactions in one pot; extended to polymers, two functionalizable sites can be introduced into different structural groups through continuous post-modification reactions, thereby giving the polymer material a variety of properties.

[0161] Test Example 9

[0162] Polymers containing alkynyl and alkenyl groups can be transformed into alkynyl and alkenyl groups through CuAAC reaction and free radical addition reaction of double bonds to introduce different functional groups. For example: first, the triazole group is introduced by reacting the alkynyl group with ethyl azidoacetate, and then the double bond is reacted with diallyl disulfide to introduce flexible alkyl chains and disulfide bonds. Self-healing materials are constructed by using various dynamic forces such as π-π stacking, dynamic disulfide bonds, and microphase separation. The CuAAC reaction of ethyl azidoacetate (above) with alkenyl and alkynyl polymers (below) was analyzed by NMR hydrogen spectrum superposition, and the results are as follows: Fig.12 As shown. Fig.12 It can be seen that after the CuAAC reaction, the alkynyl signal in the original polymer disappeared, the triazole signal appeared, and the olefinic signal remained unchanged, proving that the modification reaction can efficiently and specifically transform the alkynyl groups in the polymer without affecting other structures.

[0163] The self-healing materials prepared from alkenyl and alkyne-containing polymers were subjected to tensile superposition analysis before and after repair at 50°C for 5h. The results are as follows: Fig.13 As shown. Fig.13 It can be seen that the polymer (black) after the alkynyl and alkenyl components are modified at the same time (double-component modification) shows a good repair efficiency of 96.9%; the repair efficiency of the unmodified polymer (red) is 51.6%; the repair efficiency of the single-component modified alkynyl polymer (blue) is 59.1%; the repair efficiency of the single-component modified alkenyl polymer (green) is 49.2%. It proves that only by modifying the alkynyl and alkenyl components at the same time can good self-healing properties be achieved.

[0164] Test Example 10

[0165] Different from Examples 30 to 32 [HDEMA] 0 / [IAP-1] 0 Ratio, select polymers prepared with different Lewis acids for GPC analysis, the results are as follows Fig.14 As shown. Fig.14 It can be seen that the GPC curves of the obtained polymers are all single-peaked, and the polymers have a narrow molecular weight distribution.

[0166] Test Example 11

[0167] Combined with click reaction, polymers containing conjugated diene and alkynyl groups can be used as an efficient platform for post-modification preparation of functional polymer materials. The H NMR spectrum superposition analysis of the click reaction of poly(2,4-hexadiene) methacrylate (PHDEMA) and triazolinedione (TAD) was performed, and the results are as follows Fig.15 Comparing the NMR spectrum of poly(2,4-hexadiene) methacrylate (upper) and the NMR spectrum of triazolinedione (lower), the conjugated diene group reacts completely with triazolinedione (middle).

[0168] The polymer containing conjugated diene and alkynyl groups was subjected to sequential post-modification reaction with triazolinedione and azide compounds. The conjugated diene group was introduced into a specific functional group through the addition click reaction with triazolinedione, and the alkyne group was introduced into another specific functional group through the azide-alkyne cycloaddition (CuAAC) reaction with azide compounds. The NMR hydrogen spectrum superposition analysis of the sequential click reaction was performed, and the results are as follows Fig.16 Comparing the NMR spectra of poly(2,4-hexadiene)methacrylate after modification (top) and poly(butyl methacrylate) after modification (middle), it can be seen that after the sequential click reaction of the copolymer of (2,4-hexadiene)methacrylate and butyl methacrylate, the conjugated diene group and the alkynyl group are completely converted into specific groups (bottom).

[0169] according to Figures 15-16 It can be seen that the conjugated diene groups and alkynyl groups existing simultaneously in the system can be transformed separately through sequential reactions in one pot, that is, through continuous post-modification reactions, the two functionalizable sites can be introduced into different structural groups, thereby giving the polymer material a variety of properties.

[0170] It can be seen from the above embodiments that the present invention can catalyze the active controllable polymerization of functionalized monomers through a specific Lewis acid-base pair to obtain a polymer containing functionalized sites with a clear structure. The position and density of the functionalized sites can be easily adjusted, thereby overcoming the problem that the functionalized sites are difficult to quickly and completely convert into specific groups due to the large steric hindrance of the polymer.

[0171] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. Use of a Lewis acid-base pair in catalyzing the polymerization of a functionalizable monomer, the Lewis acid-base pair comprising a Lewis acid and a Lewis base; The Lewis base includes one or more of the Lewis base of formula NHO, the Lewis base of formula IAP, the Lewis base of formula DIAP and the Lewis base of formula PyAP; In the formula NHO, formula IAP, formula DIAP and formula PyAP, n=1-9, R1 is hydrogen, alkyl or phenyl; R2 is hydrogen, alkyl, phenyl or substituted phenyl; R3 is alkyl, phenyl or substituted phenyl; R4 is alkyl, phenyl or substituted phenyl; R5 is hydrogen, alkyl, phenyl or substituted phenyl; R6 is hydrogen, alkyl, phenyl or substituted phenyl.

2. The use according to claim 1, characterized in that: The following steps are involved: The monomer, Lewis acid-base pair and organic solvent are mixed to carry out polymerization reaction to obtain a polymer.

3. The use according to claim 2, characterized in that: The molar ratio of the monomer to the Lewis base in the Lewis acid-base pair is 15 to 50,000:

1.

4. The use according to claim 2 or 3, characterized in that: The concentration of the monomer in the mixed solution is not less than 0.2M.

5. The use according to claim 2, characterized in that: The polymerization reaction temperature is -50 to 100°C, and the heat preservation reaction time is 10s to 72h.

6. The use according to claim 2, characterized in that: The monomer includes one or more of butyl methacrylate, propargyl methacrylate and methacrylate.

7. The use according to claim 2 or 6, characterized in that: The organic solvent includes one or more of benzene homologues, furan compounds, amide compounds and substituted benzene.

8. The use according to claim 2 or 3, characterized in that: The monomer, Lewis acid-base pair and organic solvent are mixed as follows: the monomer and the first part of the organic solvent are mixed to obtain a monomer solution, the Lewis acid and the second part of the organic solvent are mixed to obtain a Lewis acid solution, the Lewis base and the third part of the organic solvent are mixed to obtain a Lewis base solution, the monomer solution, the Lewis acid solution and the remaining part of the organic solvent are mixed to obtain a premixed solution, and then the premixed solution and the Lewis base solution are mixed.

9. The use according to claim 1, characterized in that: The molar ratio of the Lewis acid to the Lewis base is not less than 2:

1.

10. The use according to claim 1, characterized in that: The Lewis acid includes one or more of the Lewis acid of formula A-1, the Lewis acid of formula A-2, the Lewis acid of formula A-3 and the Lewis acid of formula A-4; In formula A-1 to formula A-4, R1 is an alkyl group or a halogen; R2 is a hydrogen group, an alkyl group, a substituted alkyl group or a halogen; and R3 is a hydrogen group, an alkyl group or a halogen.

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