Hydrogen bond donor catalyst for active cationic polymerization and active cationic polymerization method

Abstract

The invention relates to the technical field of polymer synthesis, in particular to a hydrogen bond donor catalyst for active cationic polymerization and an active cationic polymerization method. The catalyst relates to a fluoroalcohol compound with a specific structure, is applied to active cationic polymerization, can regulate and control an electron-rich alkene monomer and other monomers capable of cationic polymerization to perform polymerization reaction under a mild condition, and dynamically and reversibly activates a dormant covalent bond through a non-covalent anion binding effect, so that the active cationic polymerization is realized. The molecular weight, distribution, end group structure and topological structure of the obtained polymerization product can be accurately controlled, no harsh reaction condition is needed, and no metal residue is generated; the catalyst provided by the invention has a simple molecular structure, is easy to remove and recycle, is easy for large-scale production, and integrates economic feasibility, catalytic efficiency and environmental sustainability.

Description

Technical Field

[0001] The invention relates to the technical field of polymer synthesis, in particular to a hydrogen bond donor catalyst for active cationic polymerization and an active cationic polymerization method. Background Art

[0002] Living cationic polymerization is one of the most basic living polymerization technologies, providing a continuous driving force for basic research in polymer materials science and technological innovation in the polymer industry (Prog. Polym. Sci. 16, 111-172 (1991); Polym. Int. 35, 1-26 (1994); Chem. Rev. 109, 5245-5287 (2009)). Since the pioneering work in the 1980s (Macromolecules 17, 265-268, (1984); Polym. Bull. 15, 317-323, (1986)), living cationic polymerization has mainly focused on the development of active controllable polymerization systems catalyzed by metal Lewis acids, based on application needs, to develop polymer materials with better performance and lower cost. The core principle is to activate the unstable covalent bonds (CX, X = halogen atoms, carboxyl groups, etc.) in dormant species through metal catalysts to convert them into cationic active species, thereby controlling the transient equilibrium conversion between the two (Chem. Rev. 109, 5245-5287 (2009)). However, due to the inherent high electrical deficiency, extremely strong hygroscopicity of metal Lewis acid centers and the inherent instability of cationic active species, controlled polymerization must usually be carried out under strict reaction conditions, such as low temperature, inert atmosphere and strict reagent purification. In addition, metal residues are inevitably present in the polymer. In fact, in terms of meeting the needs of advanced materials engineering, metal contamination and harsh reaction conditions have become long-term challenges that restrict the further development of living cationic polymerization. In addition, these reaction conditions, which are characterized by energy intensiveness and environmental unfriendliness, have also hindered the wider scientific community, such as non-professionals in the field, from making full use of living cationic polymerization methods to synthesize various structurally clear polymer materials on demand.

[0003] To this end, in the past two decades, academia and industry have developed many novel polymerization catalytic methods, aiming to achieve living cationic polymerization in a more sustainable way (Prog. Polym. Sci. 124, 101485, (2022); Prog. Polym. Sci. 145, 101736, (2023)). Among these methods, two emerging strategies based on the cationic reversible addition-fragmentation chain transfer (RAFT) mechanism and the non-covalently activated atom transfer mechanism have attracted widespread attention. In the cationic RAFT strategy, the key to control lies in the careful selection of chain transfer agents, initiators or catalysts (such as strong acid or electrochemical and photoredox catalysts), as well as reaction conditions that ensure that the rate of addition-fragmentation chain transfer exceeds the rate of chain growth. The latter strategy uses σ-hole-type catalysts such as halogen bonds, sulfur bonds, and nitrogen bonds to extract anions from cationic generators through non-covalent interactions and produce extremely low concentrations of active cationic species under mild conditions, thereby achieving living / controllable polymerization. Despite these remarkable advances, the translation of these methods into industrial applications is inherently limited by the reagents used, which are either expensive, require time-consuming multi-step preparation, or are even unstable at room temperature. Such weaknesses significantly reduce the cost-effectiveness, making these methods less competitive than traditional metal Lewis acid catalytic systems even when sustainability is considered.

[0004] Recently, Chinese patent ZL 202211024534.9 disclosed a new active cationic polymerization catalytic method, that is, a catalytic amount of hydrogen bond donor dynamically and reversibly activates dormant covalent bonds based on supramolecular anion binding, thereby precisely controlling the equilibrium transformation between dormant covalent precursors and cationic active species, thereby catalyzing electron-rich olefin monomers and other cationic polymerizable monomers for active cationic polymerization under mild conditions. Compared with the traditional metal Lewis acid catalytic method, this emerging anion-combined catalytic polymerization method has the following advantages: 1) The polymerization conditions are milder, and it is easy to achieve active / controllable polymerization at 0°C to room temperature; 2) The use of hydrogen bond donors as catalysts has a stable structure, better water and oxygen tolerance, and can be recycled; 3) The polymerized product is easier to purify, and there is no need to worry about metal residual contamination. This method provides a new development direction for solving the related problems of the unfriendly environment of traditional active cationic polymerization systems. Despite this, the hydrogen bond donor catalysts disclosed in the patent are all NH-type skeleton structures, which need to be synthesized artificially, and there are no commercial reagents yet. When used on a large scale, the cost-effectiveness is low.

[0005] Therefore, there is an urgent need to develop a new anion-bound catalytic system that combines economic feasibility, catalytic efficiency, and environmental sustainability to further expand and deepen the living cationic polymerization method of anion-bound catalysis. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a hydrogen bond donor catalyst for living cationic polymerization and a living cationic polymerization method. The hydrogen bond donor catalyst provided by the present invention can regulate electron-rich olefin monomers and other cationically polymerizable monomers to carry out living cationic polymerization under mild conditions, and accurately control the molecular weight, distribution, end group structure and topological structure of the resulting polymer product.

[0007] The present invention provides a hydrogen bond donor catalyst for living cationic polymerization, which is a fluoroalcohol compound; or, it comprises a fluoroalcohol compound and an additive;

[0008] The fluoroalcohol compound is selected from one or more compounds having the structure of Formula 1 or Formula 2;

[0009]

[0010] In Formula 1, the R is selected from C1 to C 30 Fluorinated alkyl groups;

[0011] In Formula 2, R1 to R5 are independently selected from H, F, C1 to C5 alkyl, C1 to C5 fluorinated alkyl, C1 to C5 hydroxyalkyl or C1 to C5 fluorinated hydroxyalkyl;

[0012] The X is selected from a C1-C5 alkyl group or a C1-C5 fluorinated alkyl group;

[0013] At least one of the R1 to R5 and the X is a fluorine-containing group;

[0014] a is 1, 2 or 3;

[0015] The fluorinated alkyl group of the present invention is an alkyl group having at least one fluorine atom substituted group in the group, and the fluorinated alkyl group includes a fluorinated straight-chain fatty alkyl group or a fluorinated branched fatty alkyl group. Preferably, the fluorinated alcohol compound of the present invention is selected from one or more compounds having the structure of Formula 1, Formula 2-a or Formula 2-b;

[0016]

[0017] In Formula 1, the R is selected from C1 to C 10 Fluorinated alkyl groups;

[0018] In formula 2-a, R1 to R5 are independently selected from H, F, trifluoromethane or C1 to C3 fluorine-containing hydroxyalkyl; X is selected from C1 to C3 fluorine-containing alkyl;

[0019] In formula 2-b, R1 to R5 are independently selected from H, F or trifluoromethane.

[0020] In certain embodiments of the present invention, the fluoroalcohol compound is selected from one or more compounds having structures of formula FA-1 to formula FA-24;

[0021]

[0022] The fluoroalcohol compounds of the present invention can be used alone as hydrogen bond donor catalysts for active cationic polymerization in active cationic polymerization reactions, or can be used in combination with conventional catalyst additives. Active controllable cationic polymerization can be achieved under mild conditions without the need for harsh reaction conditions (such as low temperature, inert atmosphere, and strict purification of reagents) and without metal residues.

[0023] The present invention provides a living cationic polymerization method, comprising the following steps:

[0024] In the presence of a hydrogen bond donor catalyst for living cationic polymerization and a cationic initiator, a cationic polymerization monomer is subjected to a living cationic polymerization reaction; or, in the presence of a hydrogen bond donor catalyst for living cationic polymerization, a cationic initiator and a salt, a cationic polymerization monomer is subjected to a living cationic polymerization reaction; the hydrogen bond donor catalyst for living cationic polymerization is the hydrogen bond donor catalyst for living cationic polymerization described in any of the above technical solutions.

[0025] The present invention conducts a living cationic polymerization reaction on a cationic polymerization monomer, specifically, conducts a living cationic polymerization reaction on one or more cationic polymerization monomers to form a homopolymer or a copolymer. In the living cationic polymerization reaction of the present invention, the amount and relative proportion of the cationic initiator and the hydrogen bond donor catalyst for living cationic polymerization are based on the effective living cationic polymerization. The initiation efficiency of the cationic initiator of the present invention under the action of the hydrogen bond donor catalyst for living cationic polymerization is usually very good (at least 50%, preferably 80%, and most preferably greater than or equal to 90%), so the concentration of the cationic initiator of the present invention is 10 -5 mol / L~1mol / L, preferably 10 -4 mol / L~10 - 1 mol / L; the molar ratio of the cationic initiator to the cationic polymerization monomer is (10 -4 ~10 -1 ): 1, preferably (10 -3 ~2×10 -2 ): 1; Cationic initiators with a concentration of 0.1 to 1 mol / L are particularly suitable for preparing end-group functionalized polymers.

[0026] In the living cationic polymerization reaction involved in the present invention, the molar ratio of the hydrogen bond donor catalyst for living cationic polymerization and the cationic initiator is usually a molar ratio that can effectively polymerize the selected cationic polymerization monomers. The molar ratio of the hydrogen bond donor catalyst for living cationic polymerization and the cationic initiator of the present invention is (1-10000):1, preferably (10-5000):1, more preferably (50-500):1, and most preferably (80-200):1. When used in high doses, the hydrogen bond donor catalyst for living cationic polymerization of the present invention can extract and combine its counter anion from the cationic initiator or the end of the dormant polymer chain through supramolecular anion binding to produce extremely low concentration cationic active species, realize the transient reversible conversion of dormant species and cationic active species, and promote the polymerization of cationic active species and the cationic polymerization monomers.

[0027] In the living cationic polymerization reaction of the present invention, the addition of salt can promote the reversible transformation between dormant species and active species, and shift the equilibrium to the dormant species. Therefore, in order to better control the polymerization, the molar ratio of the salt to the cationic initiator is usually (0.01-100):1, preferably (0.1-10):1, and more preferably (0.1-1):1.

[0028] The salt of the present invention is selected from one or more of quaternary ammonium salts or quaternary phosphonium salts. In certain embodiments of the present invention, the salt is selected from one or more of compounds having structures of formula S-1 to formula S-24;

[0029]

[0030] The cationic initiator of the present invention can generate cationic active species under the action of the above-mentioned hydrogen bond donor catalyst for living cationic polymerization, and the cationic initiator is selected from One or more of an acid or an adduct;

[0031] The present invention The acid is selected from one or more compounds having a H-X1 structure; wherein X1 is selected from Cl, Br, I, ClO4, BrO4, IO4, CN, N3, (C6F5)4B, SCN, NO3, PF6, BF4, SbF6,

[0032] The R 2 ~R 10 , R g ~R j and R l ~R m independently selected from hydrogen, halogen atoms, CN, SCN, NO2, C6F5, C1-C30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Halogenated fatty chain alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; said R a , R k and R c ~R f Independently, it forms C5~C with the O where it is and the P where O is 30 A substituted or unsubstituted heteroaromatic group; said R b The S where it is and the N where S is are C5~C 30 A substituted or unsubstituted heteroaromatic group; wherein, represents the substitution site of the group, the C1~C 30 The fatty chain alkyl group includes a straight chain alkyl group or a branched chain alkyl group.

[0033] In certain embodiments of the present invention, the The acid is selected from compounds having structures of formula BA-1 to formula BA-64;

[0034]

[0035]

[0036] Wherein, Ar is selected from groups having structures of formula a to formula v;

[0037]

[0038] in, represents the substitution site of the group, Ph represents phenyl, n Bu represents n-butyl, tolyl represents p-methylphenyl, Ar represents aromatic group, and Tf represents trifluoromethanesulfonyl group.

[0039] The adduct of the present invention is selected from one or more compounds having structures of formula A to formula M;

[0040]

[0041] Among them, the X2~X 12Independently selected from Cl, Br, I, ClO4, BrO4, IO4, CN, N3, (C6F5)4B, SCN, NO2, PF6, BF4, SbF6,

[0042] The R 0 ~R 10 independently selected from hydrogen, halogen atoms, CN, SCN, NO2, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; wherein, represents the substitution site of the group, the C1~C 30 The fatty chain alkyl group includes a straight chain alkyl group or a branched chain alkyl group;

[0043] The R 11 ~R 21 independently selected from hydrogen, C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group.

[0044] In certain embodiments of the present invention, the adduct is selected from compounds having structures of Formula I-1 to Formula I-57;

[0045] ;

[0046] Among them, Me represents methyl, Et represents ethyl, Ac represents acetyl, and Ph represents phenyl. n Bu represents n-butyl, and Tf represents trifluoromethanesulfonyl.

[0047] The cationic polymerizable monomer of the present invention is selected from one or more of electron-rich olefin monomers or other cationic polymerizable monomers.

[0048] The electron-rich olefin monomer of the present invention is selected from one or more compounds having a structure of Formula 3:

[0049]

[0050] Among them, the R 22 and R 23 are independently selected from hydrogen or C1-C6 alkyl, and the R 22 and R 23 At least one of them is a hydrogen atom; said R 24 and R 25 independently selected from hydrogen, C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic group, C5~C 30 Substituted or unsubstituted heteroaromatic groups, OR 26 or NR 27 R 28 ; said R 26 is C2H4OCH3, C2H4Cl, C2H4N3, tert-butyldimethylsilyloxyethyl, C1-C6 alkyl or C3-C6 aliphatic cycloalkyl; said R 27 and R 28 Independently selected from C6~C 30 A substituted or unsubstituted aromatic group, or the R 27 and R 28 It is C6~C with the N where it is located 30 A substituted or unsubstituted heteroaromatic group.

[0051] It is further preferred that the electron-rich olefin monomer is one or more of vinyl ether, isobutylene, butadiene, isoprene, styrene, styrene derivatives and vinyl carbazole.

[0052] Most preferably, the electron-rich olefin monomer is selected from one or more compounds having structures of formula M-1 to formula M-57;

[0053]

[0054] In the above structure, the symbol Indicates that the chiral stereo configuration of the substituent is R or S, or that the double bond stereo configuration is Z or E. In the above structure, Me represents methyl, Et represents ethyl, Ac represents acetyl, t Bu represents tert-butyl, nBu represents n-butyl.

[0055] The other cationic polymerizable monomers of the present invention are selected from one or more compounds having structures of Formula 4 to Formula 25;

[0056]

[0057] Wherein, n is a positive integer from 1 to 5;

[0058] The R 29 , R 35 and R 50 Independently selected from C1 to C 30 Perfluoroalkylidene, C1~C 30 Fatty chain alkylidene, C1~C 30 Aliphatic chain heteroalkylidene, C1~C 30 Substituted or unsubstituted aliphatic cycloalkylene group, C2~C 30 Alkenyl, C3~C 30 Substituted or unsubstituted heterocyclic forked group, C6~C 30 Substituted or unsubstituted aromatic formate or C5~C 30 A substituted or unsubstituted heteroaromatic formate;

[0059] The R 33 , R 34 , R 36 and R 37 independently selected from hydrogen, halogen atoms, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Chlorine-substituted fatty chain alkyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; or, said R 33 and R 34 Together with their respective Cs, the four form C1~C 30 A substituted or unsubstituted aliphatic hydrocarbon ring; or, said R 36 and R 37 Together with their respective Cs, the four form C1~C 30 A substituted or unsubstituted aliphatic hydrocarbon ring;

[0060] The R 30 ~R 32 and R38 ~R 51 independently selected from hydrogen, halogen atoms, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Chlorine-substituted fatty chain alkyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group.

[0061] In certain embodiments of the present invention, the other cationic polymerizable monomers are selected from one or more compounds having structures of formula M-58 to formula M-183;

[0062]

[0063]

[0064] The living cationic polymerization method of the present invention can be carried out in the absence of a solvent, that is, bulk polymerization can be performed. However, when a solvent is used, suitable solvents include low-polarity halogenated alkane solvents (such as methyl chloride, dichloromethane, chloroform, dichloroethane, trichloroethane, carbon tetrachloride, etc.), hydrocarbon non-polar solvents (such as n-hexane, cyclohexane), aromatic hydrocarbons (such as toluene, xylene, benzene, benzonitrile, chlorobenzene), non-polar ether solvents (such as ether, methyl cyclohexyl ether, tetrahydrofuran), and also include mixed solvents in which the above solvents are mixed in any proportion.

[0065] In the present invention, the key to controlling the living cationic polymerization reaction may include: (1) matching the reactivity of the cationic initiator with the reactivity of the cationic polymerization monomer; (2) matching the energy of bond breaking and bond formation of the dormant species with that of the fluoroalcohol catalyst; and (3) inhibiting possible chain transfer and chain termination side reactions.

[0066] The reactivity matching of the cationic initiator and the cationic polymerization monomer depends to a certain extent on the stabilizing effect of the substituent on the cation. Therefore, when the cationic polymerization monomer is a vinyl ether (e.g., isobutyl vinyl ether, ethyl vinyl ether, methyl vinyl ether, etc.), a styrene derivative, isobutylene, butadiene, isoprene, cyclic acetal, cyclic ether, cyclic thioether, cyclic disulfide, thiocarboxy lactone, etc., the aforementioned Acids can be used as cationic initiators, and the aforementioned adducts can also be selected as cationic initiators. However, the reactivity matching of the two needs to be considered during the selection process, especially for low-activity monomers. It is necessary to give priority to highly active cationic initiators (i.e., initiator structures with weak cation stabilization effects of substituents). This "matching" of the substituents on the cationic initiator and the cationic polymerization monomer provides a beneficial balance of the relative reactivity of the cationic initiator and the cationic polymerization monomer.

[0067] The energy of bond breaking and bond formation of dormant species should match that of fluoroalcohol catalysts, which requires: (1) careful design of the structure of hydrogen bond donor catalysts for living cationic polymerization, whose Lewis acidity is significantly weaker than that of metal Lewis acids, but sufficient to extract anions from the cation source, thereby retaining extremely low concentrations of cationic active species and allowing chain growth under mild conditions. (2) The hydrogen bond donor can dynamically stabilize ionic intermediates through anion binding, achieve rapid equilibrium with covalent precursors, and promote reversible transient conversion between dormant species and cationic active species. Preferably, the selection of cationic polymerization monomers, cationic initiators, and hydrogen bond donor catalysts for living cationic polymerization makes the growth rate of cationic active species generated by the cationic initiator to be X1-X higher than that of the cationic active species. 12 Group (X2~X 12 The group definition is as described above) is not less than 1000 times (preferably not less than 100 times) slower in binding rate with the cationic active end, that is, after one monomer is added, the cationic active species generated by the cationic initiator preferentially binds to its X1~X 12 The radicals react to form dormant species, allowing the polymer chains to grow evenly during the polymerization process.

[0068] In order to inhibit possible chain transfer and chain termination side reactions, it is required to construct a ternary supramolecular complex system of cationic polymerization monomers, hydrogen bond donor catalysts for active cationic polymerization, and active chain ends through anion binding, stabilize cationic intermediates and chain growth transition states, and disperse anionic charges to reduce their alkalinity, thereby inhibiting side reactions such as β-hydrogen elimination.

[0069] The living cationic polymerization reaction involved in the present invention can be carried out in an open container, a sealed container (such as a glass reaction bottle, a Schlenk polymerization tube, etc.) or in an autoclave. The temperature of the living cationic polymerization reaction of the present invention is -100°C to 200°C, preferably -78°C to 100°C, and most preferably 0°C to 25°C. The living cationic polymerization reaction of the present invention should be carried out for a sufficiently long time so that the conversion rate of cationic polymerization monomers into polymers is at least 10% (preferably at least 50%, more preferably at least 80%, and most preferably at least 95%). Usually, the living cationic polymerization reaction time is from a few seconds to 5 days, preferably from 1 minute to 3 days, and most preferably from 1 to 30 minutes.

[0070] After the polymerization step is completed, the (co)polymer formed is separated. The separation step of the present method is carried out by known procedures and may include precipitation in a suitable solvent, filtering the precipitated polymer, washing the polymer and drying the polymer. Precipitation can generally be carried out using water, a suitable C5-C8 alkane or C5-C8 cycloalkane solvent, such as pentane, hexane, heptane, cyclohexane or solvent oil, or using a C1-C6 alcohol, such as methanol, ethanol or isopropanol, or a mixture of any suitable solvent. Preferably, the solvent used for precipitation is hexane, a hexane mixture, methanol or water.

[0071] The (to) polymer of precipitation can be filtered by gravity or vacuum filtration according to known methods (e.g., using a funnel and an aspirator). If necessary, then the solvent washing polymer can be used for the precipitated polymer. The steps of precipitation, filtration and washing can be repeated as required. The (to) polymer of precipitation can also be precipitated by centrifugal collection, pouring the supernatant, and the precipitation is washed with a sedimentation solvent. The steps of precipitation, centrifugation and washing can be repeated as required.

[0072] Once isolated, the (co)polymer can be dried according to known methods (preferably by vacuum) by blowing air through the (co)polymer, by vacuum, etc. The (co)polymers of the invention can be analyzed and characterized by size exclusion chromatography, nuclear magnetic resonance spectroscopy and mass spectrometry according to known procedures.

[0073] The present invention provides a hydrogen bond donor catalyst for living cationic polymerization and a living cationic polymerization method. The hydrogen bond donor catalyst of the present invention relates to a fluoroalcohol compound of a specific structure, which is also used as an anion binding catalyst to dynamically bind and dissociate counter anions in the living cationic polymerization reaction. Various simple Acid or its adduct with monomer is used as a cationic initiator system (initiator). When used in high doses, it can regulate electron-rich olefin monomers and other cationic polymerizable monomers to undergo living cationic polymerization under mild conditions. It can dynamically and reversibly activate dormant covalent bonds through non-covalent anion binding, and then accurately control the equilibrium conversion between dormant species and cationic active species, thereby achieving active controllable cationic polymerization. The polymer molecular weight (M n Up to 2×10 5 g / mol), molecular weight distribution (M w / M n<1.15), not only can the molecular weight, distribution, end group structure and topological structure of the obtained polymer product be accurately controlled, but also strict reaction conditions (such as low temperature, inert atmosphere and strict purification of reagents) are not required, and there is no metal residue; and the hydrogen bond donor catalyst for active cationic polymerization of the present invention has a simple molecular structure and is easy to remove and recover by distillation, so that the method is easy to scale up production without considering cost, sustainability and complicated post-processing process, and integrates economic feasibility, catalytic efficiency and environmental sustainability. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is the polymerization catalysis mechanism diagram of the present invention;

[0075] Figure 2 is the H-NMR spectrum of poly(p-methoxystyrene);

[0076] Figure 3 is the MALDI-TOF-MS spectrum of poly(p-methoxystyrene);

[0077] Figure 4 This is the polymerization kinetics diagram of poly(p-methoxystyrene). DETAILED DESCRIPTION

[0078] The present invention discloses a hydrogen bond donor catalyst for active cationic polymerization and an active cationic polymerization method. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art and they are all considered to be included in the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0079] Unless otherwise indicated, all reagents used in the following examples are commercially available products and are of analytical grade.

[0080] In the following examples, the NMR spectra of the obtained polymers were measured using Burker AV-300, 400M liquid superconducting NMR spectrometers, deuterated chloroform solvent, at room temperature. The number average molecular weight was measured using a Waters 515 size exclusion chromatograph (Waters, USA).

[0081] like Figure 1 As shown, Figure 1 This is a diagram of the polymerization catalysis mechanism of the present invention.

[0082] The present invention will be further described below in conjunction with embodiments:

[0083] Example 1

[0084]

[0085] According to the above reaction formula, α-chloroisochroman (I-14) is used as an effective cationic initiator, hexafluoroisopropanol (FA-4) is used as an effective hydrogen bond donor catalyst, and tetrabutylammonium chloride (S-10) is used as a salt. Their combination can catalyze the living cationic polymerization of methoxystyrene (M-24) to achieve a polymer molecular weight (M n Up to 2×10 5 g / mol), distribution (M w / M n <1.15) and precise control of the end group structure.

[0086] The polymerization process is as follows: Unless otherwise stated, polymerizations were carried out in baked schlenk glass tubes under dry nitrogen. The polymerization reaction was initiated by sequentially adding pre-cooled initiators I-14 (dissolved in DCM, 0.02 mmol, 1 eq.) and FA-4 (dissolved in DCM, 0.4 mmol, 20 eq.) to the M-24 monomer solution (dissolved in DCM, 1 mmol, 50 eq.; additionally containing 0.2 eq. of S-10) via dry syringes. The solution was rapidly stirred at 0°C. After predetermined time intervals, aliquots were removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), by 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0087] Figure 2 is the H NMR spectrum of poly(p-methoxystyrene). Figure 3 This is the MALDI-TOF-MS spectrum of poly(p-methoxystyrene). Figure 2 As shown, the polymer 1 The isochroman group at the initiator end of the polymer can be clearly observed in the H NMR. Analysis of the NMR integral shows that the molecular weight of the obtained polymer is close to the theoretical value (6.7 kDa), indicating that the polymer chains are all initiated by the initiator α-chloroisochroman. Figure 3 The high-resolution mass spectrometry analysis results of the polymers also prove that the polymer chains are all initiated by the initiator α-chloroisochroman, and all polymer chains are quenched by methanol to form acetal chain ends. In addition, there is only one group of peaks in the high-resolution mass spectrum of the polymer, indicating that the chain transfer and chain termination side reactions are effectively suppressed during the polymerization process.

[0088] The key data of the application example are summarized in Table 1, which shows the results of the living cationic polymerization of p-methoxystyrene (M-24) using fluoroalcohol as an anion-binding catalyst under different conditions. As shown in Table 1, the effects of reaction temperature, initial monomer concentration, and polymerization solvent on the polymerization are also shown, all showing active controllable polymerization characteristics. Changing the ratio of monomer to initiator can effectively adjust the molecular weight of the polymer. The molecular weight increases linearly with the ratio of monomer to initiator, and a narrow molecular weight distribution (M w / M n <1.15). Changing the anionic structure of the salt does not affect the controllability of the polymerization. Keeping the ratio of monomer to initiator unchanged, increasing the catalyst concentration can significantly increase the polymerization rate, but does not affect the polymer molecular weight. Too high a catalyst concentration will lead to implosion and a broadening of the molecular weight distribution.

[0089] Table 1

[0090]

[0091]

[0092] a Unless otherwise specified, in the cationic polymerization of M-24 monomer, I-14 was used as a cationic initiator, FA-4 was used as a fluoroalcohol catalyst, TBACl (S-10) was used as a salt, the monomer concentration was 2.0 mol / L, the polymerization temperature was 0°C, the polymerization solvent was DCM, and the polymerization was carried out under a nitrogen atmosphere.

[0093] b Through nuclear magnetic 1 The monomer conversion was tested by H NMR.

[0094] c M n,calcd. =M r,monomer ×[M]0 / [Int.]0×Conv.+(M ICCl -M Cl )+31.03.

[0095] d A small amount of the polymerization reaction solution was taken out, quenched and then subjected to SEC analysis (THF, 35° C., polystyrene calibration).

[0096] e Toluene was used as the polymerization solvent.

[0097] f Chloroform was used as the polymerization solvent.

[0098] g TBABr(S-11) was used instead of TBACl.

[0099] hTBAI(S-12) was used instead of TBACl.

[0100] Figure 4 The polymerization kinetics diagram of poly(p-methoxystyrene) is shown in Figure 2. Figure 4 As shown, the polymerization kinetics results show that the reaction order of the monomer and initiator I-14 is first order, the reaction order of the catalyst FA-4 is fourth order, and the reaction order of the salt S-10 is -0.20 order. The overall rate equation is as shown in formula (1):

[0101] -d[M-24] / dt=k p [FA-4] 4.20 [I-14] 1.04 [S-10] -0.20 [M-24] t Formula (1)

[0102] Among them, k p is the chain growth rate constant.

[0103] The above results show that using I-14 as a cationic initiator and FA-4 as a hydrogen bond donor catalyst, it is possible to catalyze the active and controllable cationic polymerization of methoxystyrene (M-24) to achieve a polymer molecular weight (M n Up to 2×10 5 g / mol), distribution (M w / M n <1.15) and precise control of the end group structure, and the polymerization process does not require harsh reaction conditions (such as low temperature, inert atmosphere and strict purification of reagents), and the polymerization product has no metal residue.

[0104] The results of living cationic polymerization of different monomers using fluoroalcohol as anion-binding catalyst are shown in Table 2:

[0105] Table 2

[0106]

[0107]

[0108] a Unless otherwise specified, in the cationic polymerization of the monomer, I-14 was used as a cationic initiator, FA-4 was used as a fluoroalcohol catalyst, TBACl (S-10) was used as a salt, the monomer concentration was 2.0 mol / L, the polymerization temperature was 0°C, the polymerization solvent was DCM, and the polymerization was carried out under a nitrogen atmosphere.

[0109] b Through nuclear magnetic 1 The monomer conversion was tested by H NMR.

[0110] c M n,calcd. =M r,monomer ×[M]0 / [Int.]0×Conv.+(M ICCl -M Cl )+31.03.

[0111] Example 2

[0112]

[0113] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-25 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0114] Example 3

[0115]

[0116] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-26 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0117] Example 4

[0118]

[0119] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-27 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0120] Example 5

[0121]

[0122] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-28 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0123] Example 6

[0124]

[0125] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-29 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0126] Example 7

[0127]

[0128] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-19 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0129] Example 8

[0130]

[0131] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-21 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0132] Example 9

[0133]

[0134] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added to the M-2 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) in sequence through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0135] Example 10

[0136]

[0137] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-6 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0138] Embodiment 11

[0139]

[0140] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-9 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0141] Example 12

[0142]

[0143] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-14 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0144] Example 13

[0145]

[0146] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-45 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0147] Embodiment 14

[0148]

[0149] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-57 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0150] Embodiment 15

[0151]

[0152] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-58 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0153] Example 16

[0154]

[0155] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-63 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0156] Embodiment 17

[0157]

[0158] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-65 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0159] Embodiment 18

[0160]

[0161] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-68 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0162] Embodiment 19

[0163]

[0164] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-71 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0165] Embodiment 20

[0166]

[0167] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-82 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0168] Embodiment 21

[0169]

[0170] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-98 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0171] Embodiment 22

[0172]

[0173] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-108 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0174] Embodiment 23

[0175]

[0176] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-109 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0177] Embodiment 24

[0178]

[0179] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-120 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0180] Embodiment 25

[0181]

[0182] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-121 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0183] Embodiment 26

[0184]

[0185] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-130 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0186] Embodiment 27

[0187]

[0188] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-132 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0189] Embodiment 28

[0190]

[0191] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-133 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10 were also contained) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0192] Embodiment 29

[0193]

[0194] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-140 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0195] Embodiment 30

[0196]

[0197] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-147 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0198] Embodiment 31

[0199]

[0200] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-152 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0201] Embodiment 32

[0202]

[0203] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-155 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) via a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was removed and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0204] Embodiment 33

[0205]

[0206] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-163 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0207] Embodiment 34

[0208]

[0209] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-166 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0210] Embodiment 35

[0211]

[0212] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-168 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0213] Embodiment 36

[0214]

[0215] According to the above reaction formula, the pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were sequentially added to the M-172 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0216] Embodiment 37

[0217]

[0218] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-176 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0219] Embodiment 38

[0220]

[0221] According to the above reaction formula, pre-cooled initiator I-14 (dissolved in DCM, 0.02 mmol, 1 equivalent) and FA-4 (dissolved in DCM, 0.8 mmol, 40 equivalents) were added sequentially to the M-180 monomer solution (dissolved in DCM, 2 mmol, 100 equivalents; additionally containing 0.2 equivalents of S-10) through a dry syringe to initiate the polymerization reaction. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0222] Embodiment 39

[0223]

[0224] According to the above reaction formula, the polymerization reaction was initiated by sequentially adding the pre-cooled initiator I-14 (dissolved in DCM) and FA (Fluorinated alcohols) to the p-MeOSt monomer solution (dissolved in DCM and also containing S-10) through a dry syringe. The solution was rapidly stirred at 0°C. After a predetermined time interval, an aliquot was taken and terminated with pre-cooled methanol (0.10 mL) containing a small amount of Et3N (5% v / v in MeOH), and the reaction mixture was stirred for 2 hours. 1 The monomer conversion was determined by H NMR spectroscopy and the molecular weight was determined by size exclusion chromatography (SEC). To obtain the isolated polymer, the solution was precipitated with cold methanol and the resulting product was isolated by centrifugation and dried under vacuum for 24 hours.

[0225] Among them, FA was tested using the following compounds, and the results are listed in Table 3:

[0226]

[0227] Table 3

[0228]

[0229] a Unless otherwise specified, in the cationic polymerization of the monomer, ICl (I-14) was used as a cationic initiator, FA-4 was used as a fluoroalcohol catalyst, TBACl (S-10) was used as a salt, the monomer concentration was 2.0 mol / L, the polymerization temperature was 0°C, the polymerization solvent was DCM, and the polymerization was carried out under a nitrogen atmosphere.

[0230] b Through nuclear magnetic 1 The monomer conversion was tested by H NMR.

[0231] c M n,calcd. =M r,monomer ×[M]0 / [Int.]0×Conv.+(M ICCl -M Cl )+31.03.

[0232] d A small amount of polymerization reaction liquid was taken out, quenched and then subjected to SEC test (THF, 35°C, polystyrene calibration)

[0233] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A hydrogen bond donor catalyst for living cationic polymerization, characterized in that: It is a fluoroalcohol compound; or, it includes a fluoroalcohol compound and an additive; The fluoroalcohol compound is selected from one or more compounds having the structure of Formula 1 or Formula 2; In Formula 1, the R is selected from C1 to C 30 Fluorinated alkyl groups; In Formula 2, R1 to R5 are independently selected from H, F, C1 to C5 alkyl, C1 to C5 fluorinated alkyl, C1 to C5 hydroxyalkyl or C1 to C5 fluorinated hydroxyalkyl; The X is selected from a C1-C5 alkyl group or a C1-C5 fluorinated alkyl group; At least one of the R1 to R5 and the X is a fluorine-containing group; The a is 1, 2 or 3.

2. The hydrogen bond donor catalyst for living cationic polymerization according to claim 1, characterized in that The fluoroalcohol compound is selected from one or more compounds having the structure of Formula 1, Formula 2-a or Formula 2-b; In Formula 1, the R is selected from C1 to C 10 Fluorinated alkyl groups; In formula 2-a, R1 to R5 are independently selected from H, F, trifluoromethane or C1 to C3 fluorine-containing hydroxyalkyl; X is selected from C1 to C3 fluorine-containing alkyl; In formula 2-b, R1 to R5 are independently selected from H, F or trifluoromethane.

3. The hydrogen bond donor catalyst for living cationic polymerization according to claim 1, characterized in that The fluoroalcohol compound is selected from one or more compounds having structures of formula FA-1 to formula FA-24; 4. A living cationic polymerization method, characterized in that: The following steps are involved: In the presence of a hydrogen bond donor catalyst for living cationic polymerization and a cationic initiator, a cationic polymerization monomer is subjected to a living cationic polymerization reaction; or, in the presence of a hydrogen bond donor catalyst for living cationic polymerization, a cationic initiator and a salt, a cationic polymerization monomer is subjected to a living cationic polymerization reaction, wherein the salt is selected from one or more of a quaternary ammonium salt or a quaternary phosphonium salt; The hydrogen bond donor catalyst for living cationic polymerization is the hydrogen bond donor catalyst for living cationic polymerization as claimed in any one of claims 1 to 3.

5. The living cationic polymerization method according to claim 4, characterized in that: The cationic initiator concentration is 10 -5 mol / L~1mol / L; The molar ratio of the cationic initiator to the cationic polymerization monomer is (10 -4 ~10 -1 ):1; The molar ratio of the hydrogen bond donor catalyst for living cationic polymerization to the cationic initiator is (1 to 10000): 1; The molar ratio of the salt to the cationic initiator is (0.01-100):

1.

6. The living cationic polymerization method according to claim 4 or 5, characterized in that: The cationic initiator is selected from One or more of an acid or an adduct; Said The acid is selected from one or more compounds having the structure H-X1; Wherein, X1 is selected from Cl, Br, I, ClO4, BrO4, IO4, CN, N3, (C6F5)4B, SCN, NO3, PF6, BF4, SbF6, The R 2 ~R 10 , R g ~R j and R l ~R m independently selected from hydrogen, halogen atoms, CN, SCN, NO2, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Halogenated fatty chain alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; said R a , R k and R c ~R f Independently, it forms C5~C with the O where it is and the P where O is 30 A substituted or unsubstituted heteroaromatic group; said R b The S where it is and the N where S is are C5~C 30 A substituted or unsubstituted heteroaromatic group; The adduct is selected from one or more compounds having structures of formula A to formula M; Among them, the X2~X 12 Independently selected from Cl, Br, I, ClO4, BrO4, IO4, CN, N3, (C6F5)4B, SCN, NO2, PF6, BF4, SbF6, The R 0 ~R 10 independently selected from hydrogen, halogen atoms, CN, SCN, NO2, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; The R 11 ~R 21 independently selected from hydrogen, C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group.

7. The living cationic polymerization method according to claim 6, characterized in that: Said The acid is selected from compounds having structures of formula BA-1 to formula BA-64; Wherein, Ar is selected from groups having structures of formula a to formula v; The adduct is selected from compounds having structures of Formula I-1 to Formula I-57; 8. The living cationic polymerization method according to claim 4 or 5, characterized in that: The salt is selected from one or more compounds having structures of formula S-1 to formula S-24; 9. The living cationic polymerization method according to claim 4 or 5, characterized in that: The cationic polymerizable monomer is selected from one or more of electron-rich olefin monomers or other cationic polymerizable monomers; The electron-rich olefin monomer is selected from one or more compounds having a structure of Formula 3: Among them, the R 22 and R 23 are independently selected from hydrogen or C1-C6 alkyl, and the R 22 and R 23 At least one of them is a hydrogen atom; The R 24 and R 25 independently selected from hydrogen, C1-C 30 Alkyl, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic group, C5~C 30 Substituted or unsubstituted heteroaromatic group, OR 26 or NR 27 R 28 ; said R 26 is C2H4OCH3, C2H4Cl, C2H4N3, tert-butyldimethylsilyloxyethyl, C1-C6 alkyl or C3-C6 aliphatic cycloalkyl; said R 27 and R 28 Independently selected from C6~C 30 A substituted or unsubstituted aromatic group, or the R 27 and R 28 It is 6~C with the N where it is located 30 A substituted or unsubstituted heteroaromatic group; The other cationic polymerizable monomers are selected from one or more compounds having structures of Formula 4 to Formula 25; Wherein, n is a positive integer from 1 to 5; The R 29 , R 35 and R 50 Independently selected from C1 to C 30 Perfluoroalkylidene, C1~C 30 Fatty chain alkylidene, C1~C 30 Aliphatic chain heteroalkylidene, C1~C 30 Substituted or unsubstituted aliphatic cycloalkylene group, C2~C 30 Alkenyl, C3~C 30 Substituted or unsubstituted heterocyclic forked group, C6~C 30 Substituted or unsubstituted aromatic formate or C5~C 30 A substituted or unsubstituted heteroaromatic formate; The R 33 , R 34 , R 36 and R 37 independently selected from hydrogen, halogen atoms, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Chlorine-substituted fatty chain alkyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group; or, said R 33 and R 34 Together with their respective Cs, the four form C1~C 30 A substituted or unsubstituted aliphatic hydrocarbon ring; or, said R 36 and R 37 Together with their respective Cs, the four form C1~C 30 A substituted or unsubstituted aliphatic hydrocarbon ring; The R 30 ~R 32 and R 38 ~R 51 independently selected from hydrogen, halogen atoms, C6F5, C1-C 30 Perfluoroalkyl, C1~C 30 Fatty chain alkyl, C1~C 30 Chlorine-substituted fatty chain alkyl, C1~C 30 Substituted or unsubstituted aliphatic cyclic hydrocarbon group, C2~C 30 Alkenyl, C2~C 30 Alkynyl, C3~C 30 Substituted or unsubstituted heterocyclic group, C6~C 30 Substituted or unsubstituted aromatic or C5~C 30 A substituted or unsubstituted heteroaromatic group.

10. The living cationic polymerization method according to claim 9, characterized in that: The electron-rich olefin monomer is selected from one or more compounds having structures of formula M-1 to formula M-57; Among them, the symbol Indicates that the chiral stereo configuration of the substituent is R or S, or the double bond stereo configuration is Z or E; The other cationic polymerizable monomers are selected from one or more compounds having structures of formula M-58 to formula M-183;

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