Process for obtaining different polar monomer copolymers and homopolymers by means of catalyst composition

Abstract

The invention discloses a method for obtaining different polar monomer copolymers and homopolymers through a catalyst composition, and particularly provides a catalyst composition composed of alkyl aluminum, organic boron salt and a catalyst. The composition can catalyze a block copolymerization reaction between a polymer with a repetitive unit as shown in a formula IV and a compound M to obtain a block copolymer III, the compound M can also be catalyzed to be subjected to polymerization reaction to obtain a polymer I with a repetitive unit as shown in the formula A. According to the method, coordination polymerization of polar monomers can be efficiently catalyzed, the used catalyst is high in stability, and the homopolymer and the block copolymer which are clear in structure can be obtained at high yield; the obtained polymer has a high glass transition temperature, and part of the polymer presents a dual glass transition behavior. .

Description

Technical Field

[0001] This invention belongs to the field of polar olefin polymerization and relates to a method for obtaining copolymers and homopolymers of monomers with different polarities through a catalyst composition. Background Technology

[0002] Research on polyconjugated dienes, especially polyisoprene, has always been a hot topic and a challenge in the field of olefin polymerization. Existing research indicates that the physical properties of polyisoprene products have certain limitations, such as their relatively low glass transition temperature, with a maximum of only 40°C. o For example, its Young's modulus is very small; even isoprene of the same grade (3,4) can only reach 500 MPa. This narrows the application range of isoprene, limiting it to rubber products rather than thermoplastic materials.

[0003] Introducing polar groups into the polyisoprene chain is one method to change the properties of polyisoprene. This can be achieved by designing novel polar conjugated diene monomers and studying the homopolymerization reaction of these monomers. In addition, copolymerization of polar monomers is also an important method to change polymer properties. For example, adding polar monomers can change the surface morphology, viscosity, glass transition temperature, and sprayability of the product. Therefore, designing and synthesizing novel polar conjugated diene monomers, studying the homopolymerization of these monomers, and copolymerizing them with other polar monomers are important research directions with both theoretical and practical significance. However, the copolymerization of polar monomers currently faces the following core challenges: (1) The electronic effects and steric hindrance of polar groups significantly affect the reactivity of the monomers, leading to uneven copolymer composition; (2) Polar groups (such as ester groups and carboxyl groups) are prone to strong coordination with metal centers, leading to catalyst deactivation.

[0004] In recent years, research on the application of rare earth metal catalysts in the field of polar monomer copolymerization has continued to advance, achieving several representative results. For example, in 1993, Yasuda's group reported the successful preparation of acrylate-type block copolymers using the rare earth metal catalyst (C5Me5)2LnMe(THF) (Ln = Sm, Y). In 2010, Bernhard Rieger's group first successfully synthesized MMA / DEVP block copolymers by sequentially adding two monomers using the rare earth metal complex [Cp2YbMe]. Currently, many polar functional group-substituted conjugated olefins, such as silicon-based, cyano-based, halogen-based, and amino-based conjugated olefins, have been synthesized, but their homopolymers can only be obtained through free radical polymerization or anionic polymerization. Moreover, these polymerization methods cannot control the regio- and stereoselectivity of the reaction. In coordination polymerization, heteroatoms often readily coordinate with the central metal, thus poisoning the active material. This prevents conventional rare-earth metal catalysts from effectively catalyzing the coordination polymerization of such polar monomers, severely limiting the industrial preparation and application of polar modified polyconjugated dienes. It wasn't until 2016 that the homopolymerization of oxygen-heteroatom-substituted conjugated dienes catalyzed by rare-earth coordination compounds was reported.

[0005] As good alternatives to locene ligands, amidine and guanidine ligands have many advantages, such as the ease of introducing various substituents on C or N atoms to regulate the electronic effects or steric hindrance of the ligands, resulting in rare earth organometallic compounds with broad research prospects. Summary of the Invention

[0006] The technical problem this invention aims to solve is to overcome the shortcomings of existing technologies, such as the homopolymerization of polar conjugated diene monomers and the limited selectivity and easy deactivation of catalysts in copolymerization of polar conjugated diene monomers with polar monomers. This invention provides a method for obtaining copolymers and homopolymers of different polar monomers through a catalyst composition, a catalyst composition, and corresponding homopolymers and copolymers. This preparation method achieves high yield, high regioselectivity, and stereoselectivity in the coordination polymerization of polar monomers through a highly efficient and stable catalytic system. The method has a wide reaction temperature window, controllable polymerization process, and adjustable glass transition temperatures for both homopolymers and block copolymers. The resulting copolymers exhibit both high glass transition temperatures and high elastic moduli, demonstrating excellent mechanical properties.

[0007] The present invention solves the above-mentioned technical problems through the following technical solution: The present invention provides a method for preparing polymer I, which includes the following steps: in an organic solvent, in the presence of a compound as shown in formula IIa, an organoboron salt and an alkylaluminum, compound M undergoes a polymerization reaction to obtain polymer I having repeating units as shown in formula A; in, The compound M is a compound as shown in formula Ma, and the repeating unit as shown in formula A is a repeating unit as shown in formula Aa. Alternatively, the compound M is a compound of formula Mb, and the repeating unit of formula A is a repeating unit of formula Ab. ; R 1 Independently for C 1-6 alkyl; R 2 Independently for H and C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; R Ar C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 3 Replacement C 6-10 Aromatic rings; R 3 Independently for C 1-6 Alkyl, -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl; RE is one or more of scandium (Sc), yttrium (Y), and all lanthanides.

[0008] In one particular scheme, R Ar In, the C 6-10 Aromatic rings and 1, 2 or 3 R 3 Replacement C 6-10 In the aromatic ring, the C 6-10 The aromatic ring is a benzene ring.

[0009] In one particular scheme, R 3 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0010] In one particular scheme, R 3 In the context, the -OC 1-6 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0011] In one particular scheme, R 3 In the context, the C substituted with one, two, or three halogens 1-6 In alkyl groups, the C 1-6The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0012] In one particular scheme, R 3 In the context, the C substituted with one, two, or three halogens 1-6 In the alkyl group, the halogen is F, Cl, Br or I, for example F.

[0013] In one particular scheme, R 3 In the context, the C substituted with one, two, or three halogens 1-6 The alkyl group is trifluoromethyl.

[0014] In one particular scheme, R 3 Independently for -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl.

[0015] In one scheme, RE is scandium (Sc), yttrium (Y), lanthanum (La), or lutetium (Lu), for example, yttrium (Y), lanthanum (La), or lutetium (Lu).

[0016] In one embodiment, the compound represented by formula IIa is any of the structures shown in formulas 1-6: .

[0017] In one particular scheme, R 1 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl or isopropyl.

[0018] In one particular scheme, R 2 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0019] In one particular scheme, R 2 In the context, the -OC 1-6 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy.

[0020] In one particular scheme, R 2 In the context, the C substituted with 1, 2, or 3 halogens 1-6 Alkyl or -OC 1-6 In the alkyl group, the halogen is F, Cl, Br or I, for example F.

[0021] In one particular scheme, R 2 In the context, the C substituted with 1, 2, or 3 halogens 1-6The alkyl group is trifluoromethyl.

[0022] In one particular scheme, R 2 Independently H, -OC 1-6 Alkyl groups or C atoms substituted with 1, 2 or 3 halogens 1-6 alkyl.

[0023] In one particular scheme, R 1 It can be methyl or isopropyl on its own.

[0024] In one particular scheme, R 2 It can be H, methoxy, or trifluoromethyl independently.

[0025] In one embodiment, the molecular weight distribution index of polymer I is 1-2, preferably 1.2-1.8, more preferably 1.4-1.8, for example 1.76, 1.73, 1.56, 1.63, 1.71, 1.78, 1.79, 1.42, 1.45, 1.44, 1.66 or 1.6.

[0026] In one embodiment, the number-average molecular weight of polymer I is 5000-40000 g / mol, preferably 6000-36000 g / mol, for example 6384 g / mol, 6993 g / mol, 7059 g / mol, 9879 g / mol, 10697 g / mol, 9719 g / mol, 10049 g / mol, 10352 g / mol, 35050 g / mol, 17181 g / mol, 34116 g / mol, or 22300 g / mol.

[0027] In one embodiment, the preparation method of polymer I includes repeating units formed by 1,2-addition and repeating units formed by 1,4-addition (i.e., repeating units as shown in formula Aa or formula Ab).

[0028] In one embodiment, the polymer I is a homopolymer in the preparation method of polymer I.

[0029] In one embodiment, in the preparation method of polymer I, the molar percentage of repeating units formed by 1,4-addition in polymer I is 90-99%, for example 90%, 91%, 92%, 93%, 94% or 95%.

[0030] In one embodiment, the method for preparing polymer I includes a repeating unit as shown in formula Aa. or .

[0031] In one embodiment, the method for preparing polymer I includes a repeating unit as shown in formula Ab. or .

[0032] In one embodiment, in the preparation method of polymer I, the repeating unit in polymer I... and repeating units Random distribution.

[0033] In one embodiment, in the method for preparing polymer I, the polymer contains repeating units. and repeating units Random distribution.

[0034] In one embodiment, the method for preparing polymer I is a polymer as shown in formula Ia or a polymer as shown in formula Ib: ; Wherein, o is selected from 1-500, preferably 1-200, and more preferably 30-170.

[0035] In one embodiment, in the preparation method of polymer I, polymer I is a polymer as shown in formula Ic or a polymer as shown in formula Id; ; m is selected from 1-500; n is selected from 1-500; p is selected from 1-500.

[0036] In one embodiment, the compound shown in formula Ma has the following structure in the preparation method of polymer I; .

[0037] In one embodiment, in the preparation method of polymer I, the compound represented by formula Mb has any of the following structures; , , or .

[0038] In one embodiment, in the preparation method of polymer I, the repeating unit shown in formula Aa is a repeating unit shown in formula Aa-4: .

[0039] In one embodiment, in the method for preparing polymer I, the repeating unit as shown in formula Ab is any repeating unit as shown in formula Ab-1, Ab-2, Ab-3, or Ab-6: , , or .

[0040] In one embodiment, the end groups of polymer I are conventional in the art, preferably H or alkyl.

[0041] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.76, the number-average molecular weight is 6384 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 94%.

[0042] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.73, the number-average molecular weight is 6993 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 93%.

[0043] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.56, the number average molecular weight is 7059 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 93%.

[0044] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.63, the number-average molecular weight is 9879 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 93%.

[0045] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.71, the number-average molecular weight is 10697 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 93%.

[0046] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.78, the number average molecular weight is 9717 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 90%.

[0047] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.79, the number average molecular weight is 10049 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 93%.

[0048] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-2, the molecular weight distribution index of polymer I is 1.42, the number-average molecular weight is 10352 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 90%.

[0049] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-3, the molecular weight distribution index of polymer I is 1.45, the number average molecular weight is 35050 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 91%.

[0050] In one embodiment, in polymer I, the repeating unit as shown in formula A is a repeating unit as shown in formula Aa-4, the molecular weight distribution index of polymer I is 1.44, the number average molecular weight is 17181 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 95%.

[0051] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-6, the molecular weight distribution index of polymer I is 1.66, the number-average molecular weight is 34116 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 99%.

[0052] In one embodiment, in polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Ab-1, the molecular weight distribution index of polymer I is 1.6, the number average molecular weight is 22300 g / mol, and the molar percentage of repeating units formed by 1,4-addition in polymer I is 92%.

[0053] In one embodiment, the repeating unit shown in formula Ab is a repeating unit shown in formula Ab-1, and the polymer I is... .

[0054] In one embodiment, the repeating unit shown in formula Ab is the repeating unit shown in formula Ab-2, and the polymer I is... .

[0055] In one embodiment, the repeating unit shown in formula Ab is the repeating unit shown in formula Ab-3, and the polymer I is... .

[0056] In one embodiment, the repeating unit shown in formula Aa is a repeating unit shown in formula Aa-4, and the polymer I is... .

[0057] In one embodiment, the repeating unit shown in formula Ab is the repeating unit shown in formula Ab-6, and the polymer I is... .

[0058] In one embodiment, the organic solvent used in the preparation method of polymer I is an aromatic hydrocarbon solvent. The aromatic hydrocarbon solvent is preferably toluene.

[0059] In one embodiment, in the preparation method of polymer I, the molar volume ratio of compound M to organic solvent is (0.1-1) mol / L, preferably (0.1~0.5) mol / L, for example 0.21 mol / L.

[0060] In one embodiment, in the preparation method of polymer I, the alkyl aluminum is trimethylaluminum, triethylaluminum, or triisopropylaluminum, such as trimethylaluminum.

[0061] In one embodiment, in the preparation method of polymer I, the alkyl aluminum is used in solution form, preferably in the form of an alkyl aluminum n-hexane solution, and more preferably in the form of a 1M concentration alkyl aluminum n-hexane solution.

[0062] In one embodiment, in the preparation method of polymer I, the molar ratio of the alkylaluminum to the compound represented by formula IIa is (1~10):1, for example 5:1.

[0063] In one embodiment, the organic boron salt used in the preparation method of polymer I is an arylborate. The arylborate is preferably a tetraarylborate. The tetraarylborate is preferably [Ph3C][B(C6F5)4].

[0064] In one embodiment, in the preparation method of polymer I, the molar ratio of the organoboron salt to the compound shown in formula IIa is (1~10):1, for example 1:1.

[0065] In one embodiment, in the preparation method of polymer I, the molar ratio of the compound represented by formula IIa to the compound M is 1:(10~100), for example 1:50.

[0066] In one embodiment, in the preparation method of polymer I, the molar ratio of the compound represented by formula IIa, the alkylaluminum and the organoboron salt is 1:(1-10):(1-10), preferably 1:5:1.

[0067] In one embodiment, the reaction temperature in the preparation method of polymer I is 0-50℃, preferably 10-35℃.

[0068] In one embodiment, the reaction time of the polymer I preparation method is 1-180 minutes, for example 5 or 180 minutes.

[0069] In one embodiment, the reaction in the preparation method of polymer I is carried out under anhydrous and oxygen-free conditions.

[0070] In one embodiment, the reaction in the preparation method of polymer I is carried out under normal pressure.

[0071] In one embodiment, the preparation method of polymer I preferably includes the following steps: under anhydrous and oxygen-free conditions, compound M is dissolved in the organic solvent, the alkyl aluminum is added, the mixture is stirred, and then a mixed solution of the compound of formula IIa and the organic solvent, as well as a mixed solution of the organoboron reagent and the organic solvent are added sequentially to carry out the reaction.

[0072] In one embodiment, the preparation method of polymer I further includes the following post-processing steps: after the reaction is completed, the reaction is quenched by mixing with an acid, then mixed with an alcohol solvent to precipitate a solid, and then dried.

[0073] In one embodiment, during the preparation method of polymer I, the acid in the post-treatment is an alcoholic solution of hydrochloric acid. Preferably, the acid is a hydrochloric acid-methanol solution. More preferably, the acid is a 20% hydrochloric acid-methanol solution.

[0074] In one embodiment, in the preparation method of polymer I, the alcohol solvent in the post-processing is methanol or ethanol; for example, methanol.

[0075] In one embodiment, the preparation method of polymer I comprises the reactants consisting of compound M, the organic solvent, the compound represented by formula IIa, the organoboron salt, and the alkylaluminum.

[0076] In one embodiment, the preparation method of polymer I satisfies the following condition: the compound M is of formula M. 1 -M 4 and M 6The compound is any structure of the compound shown; the organic solvent is toluene; the compound shown in formula IIa is any structure of the compounds shown in formulas 1-6; the organoboron salt is [Ph3C][B(C6F5)4]; the alkylaluminum is an AlMe3 n-hexane solution; the molar volume ratio of compound M to the organic solvent is 0.2-0.21 mol / L; the molar ratio of the compound shown in formula IIa to compound M is 1:50; the molar ratio of the organoboron salt to the compound shown in formula IIa is 1:1.

[0077] The present invention also provides a polymer I having repeating units as shown in formula Aa or repeating units as shown in formula Ab.

[0078] The polymer I can be any of the preparation methods described above.

[0079] In one embodiment, polymer I is thermoplastic.

[0080] In one embodiment, the polymer I is mainly composed of repeating units as shown in Formula IV; wherein "mainly" means that the molar percentage of the repeating units as shown in Formula IV in the polymer I is greater than 90%, preferably greater than 95%.

[0081] In one embodiment, polymer I is a homopolymer.

[0082] The present invention also provides a polymer I, which is prepared by the method described above.

[0083] The present invention also provides a method for preparing block copolymer III, comprising the following steps: in an organic solvent, in the presence of alkylaluminum, organoboron salt and a compound as shown in formula IIb, a polymer having repeating units as shown in formula IV and compound M undergo a block copolymerization reaction to obtain block copolymer III; wherein the block copolymer III has repeating units as shown in formula IV and repeating units as shown in formula A. ; ; in, R 1 C 1-6 alkyl; R 2 For H, C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; R 4 C 1-6 alkyl; R5 For H or C 1-6 alkyl; Re is scandium (Sc).

[0084] In the preparation method of the block copolymer III, R 1 and R 2 It can be any of the methods described in the preparation method of polymer I as above.

[0085] In one embodiment, the block copolymer III is a binary block copolymer in the preparation method of the block copolymer III.

[0086] In one embodiment, the polymer having repeating units as shown in Formula IV is an active segment.

[0087] In one embodiment, in the method for preparing the block copolymer III, the first block of the block copolymer III has repeating units as shown in Formula IV, and the second block has repeating units as shown in Formula A.

[0088] In one embodiment, the block copolymer III is prepared in a method where the number average molecular weight is 1000-100000 g / mol, preferably 10000-60000 g / mol, more preferably 10100-56900 g / mol, for example 10100 g / mol, 10800 g / mol, 23400 g / mol, 18200 g / mol, 22800 g / mol or 56900 g / mol.

[0089] In one embodiment, the block copolymer III is prepared in a method where the molecular weight distribution index of the block copolymer III is 1-2, preferably 1.1-1.7, more preferably 1.5-1.7, for example 1.5, 1.6 or 1.7.

[0090] In one embodiment, in the preparation method of the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV in the block copolymer III is 10-90%, preferably 15-85%, for example 18.4%, 47.6%, 67.1%, 48.5%, 64.2% or 83.0%.

[0091] In one embodiment, the glass transition temperature of the block copolymer III is 30-150°C; preferably 50-150°C, more preferably 50-135°C, and even more preferably 60-135°C.

[0092] In one embodiment, the block copolymer III is prepared by a method that the block copolymer III has two glass transition temperatures, T1 and T2, where T1 is 60-80°C and T2 is 110-135°C; preferably, T1 is 62.6°C, 66.8°C, or 76.0°C, and T2 is 116.1°C, 122.1°C, or 130.2°C; more preferably, T1 is 62.6°C and T2 is 116.1°C; T1 is 66.8°C and T2 is 122.1°C; or T1 is 76.0°C and T2 is 130.2°C.

[0093] In one embodiment, in the method for preparing the block copolymer III, the molar percentage of repeating units (i.e., repeating units as shown in Formula A) formed by 1,4-addition in the blocks derived from the compound M of the block copolymer III is 90%-100%, preferably 92-95%, more preferably 93-95%, for example 92%, 93%, 94% or 95%.

[0094] In one embodiment, in the method for preparing the block copolymer III, the molar percentage of syndiotactic stereotype (rr) in the blocks having repeating units as shown in Formula IV is 70-80%, preferably 73-77%, more preferably 73-76%, for example 73%, 74%, 75%, 76% or 77%.

[0095] In one particular scheme, R 4 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0096] In one particular scheme, R 5 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl.

[0097] In one embodiment, the repeating unit shown in Formula IV in the preparation method of the block copolymer III is as follows: .

[0098] In one embodiment, the method for preparing the block copolymer III comprises compound M having the following structure: .

[0099] In one embodiment, the repeating unit shown in Formula A in the preparation method of the block copolymer III is as follows: .

[0100] In one embodiment, in the method for preparing the block copolymer III, the block copolymer III is... ; v is selected from 1-1000, preferably 10-500, more preferably 10-450, and even more preferably 60-450; w is selected from 1-1000, preferably 10-500, more preferably 10-100, and even more preferably 40-90.

[0101] In one embodiment, the block copolymer III is prepared by a method comprising the following polymer: ; u is selected from 1-1000, preferably from 10-500; t is selected from 1-1000, preferably from 10-500; x is selected from 1 to 1000, preferably from 10 to 500.

[0102] In one embodiment, the polymer having repeating units as shown in Formula IV in the preparation method of the block copolymer III has the following structure: ; S is selected from 1-1000.

[0103] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 10,100 g / mol and a molecular weight distribution index of 1.6. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 18.4%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 93%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 75%.

[0104] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 10,800 g / mol and a molecular weight distribution index of 1.6. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 47.6%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 92%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 74%.

[0105] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 23,400 g / mol and a molecular weight distribution index of 1.7. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 67.1%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 94%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 77%.

[0106] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 18200 g / mol and a molecular weight distribution index of 1.5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 48.5%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 95%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 76%.

[0107] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 22,800 g / mol and a molecular weight distribution index of 1.5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 64.2%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 93%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 73%.

[0108] In one embodiment, the method for preparing the block copolymer III includes the repeating unit shown in Formula IV as follows: The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 56,900 g / mol and a molecular weight distribution index of 1.5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 83%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 94%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic (rr) is 74%.

[0109] In one embodiment, the end groups of polymer III are conventional in the art, preferably H or alkyl.

[0110] In one embodiment, the organic solvent used in the preparation method of the block copolymer III is an aromatic hydrocarbon solvent. Toluene is preferably the aromatic hydrocarbon solvent.

[0111] In one embodiment, in the method for preparing the block copolymer III, the molar ratio of the compound as shown in Formula IIb to the volume of the organic solvent is 0.001-0.01 mol / L, preferably 0.004-0.006 mol / L, for example 0.005 mol / L.

[0112] In one embodiment, the alkylaluminum in the preparation method of the block copolymer III is trimethylaluminum, triethylaluminum, or triisopropylaluminum, such as trimethylaluminum.

[0113] In one embodiment, in the method for preparing the block copolymer III, the alkyl aluminum is used in solution form, preferably in the form of an alkyl aluminum n-hexane solution, and more preferably in the form of a 1M concentration alkyl aluminum n-hexane solution.

[0114] In one embodiment, the molar ratio of the alkylaluminum to the compound shown in formula IIb is (1~10):1, for example, 5:1.

[0115] In one embodiment, the method for preparing the block copolymer III uses an arylborate as the organoborate. The arylborate is preferably a tetraarylborate. The tetraarylborate is preferably [Ph3C][B(C6F5)4].

[0116] In one embodiment, in the preparation method of the block copolymer III, the molar ratio of the organoboron salt to the compound shown in formula IIb is (1~10):1, for example 1:1.

[0117] In one embodiment, in the preparation method of the block copolymer III, the molar ratio of the compound shown in formula IIb to the compound M is 1:(10~500), preferably 1:(50~150), for example 1:100.

[0118] In one embodiment, the molar ratio of the polymer having repeating units as shown in Formula IV to compound M in the preparation method of the block copolymer III is conventional in the art.

[0119] In one embodiment, in the preparation method of the block copolymer III, the molar ratio of the compound as shown in formula IIb, the alkyl aluminum and the organoboron salt is 1:(1-10):(1-10), preferably 1:5:1.

[0120] In one embodiment, in the preparation method of the block copolymer III, the reaction temperature of the copolymerization reaction is -78-50℃, preferably -45-35℃, more preferably -45-(-15)℃ or 10-35℃, for example -30℃ or 20-30℃, and more preferably -30℃.

[0121] In one embodiment, the copolymerization reaction time in the preparation method of the block copolymer III is 1-240 minutes, preferably 30-90 minutes, for example 60 minutes.

[0122] In one embodiment, the copolymerization reaction is carried out under anhydrous and oxygen-free conditions in the preparation method of the block copolymer III.

[0123] In one embodiment, the copolymerization reaction is carried out under normal pressure in the preparation method of the block copolymer III.

[0124] In one embodiment, the preparation method of the block copolymer III preferably includes the following steps: mixing a compound as shown in Formula IIb, a polymer having repeating units as shown in Formula IV, an organic solvent, and a mixed solution of alkyl aluminum with compound M, followed by mixing with a mixed solution of the organoboron salt and the organic solvent to undergo a copolymerization reaction, thereby obtaining the block copolymer III.

[0125] In one embodiment, the preparation method of the block copolymer III further includes the following post-processing step: after the reaction is completed, it is mixed with an alcohol solvent to precipitate a solid, which is then dried.

[0126] In one embodiment, the alcohol solvent in the post-processing is methanol or ethanol; for example, methanol.

[0127] In one embodiment, the method for preparing the block copolymer III further includes a method for preparing the polymer having repeating units as shown in Formula IV, comprising the following steps: In an organic solvent, in the presence of the compound shown in Formula IIb, the compound shown in Formula IVa undergoes a polymerization reaction to obtain the polymer having the repeating unit shown in Formula IV. ; Wherein, the R 4 R 5 The polymers of compounds as shown in Formula IIb and repeating units as shown in Formula IV are defined as described in any of the above schemes.

[0128] In one embodiment, in the method for preparing the polymer having repeating units as shown in Formula IV, the organic solvent is an aromatic hydrocarbon solvent. The aromatic hydrocarbon solvent is preferably toluene.

[0129] In one embodiment, in the method for preparing the polymer having repeating units as shown in Formula IV, the molar ratio of the compound shown in Formula IIb to the volume of the organic solvent is 0.001-0.05 mol / L, preferably 0.008-0.012 mol / L, for example 0.01 mol / L.

[0130] In one embodiment, in the method for preparing the polymer having repeating units as shown in Formula IV, the molar ratio of the compound shown in Formula IIb to the compound shown in Formula IVa is 1:(1~1000), preferably 1:(10~500), and more preferably 1:(100~400).

[0131] In one embodiment, in the method for preparing the polymer having repeating units as shown in Formula IV, the reaction temperature is -78-50°C, preferably -45-35°C, more preferably -45-(-15)°C or 10-35°C, for example -30°C or 20-30°C.

[0132] In one embodiment, the method for preparing the polymer having repeating units as shown in Formula IV includes the following steps: mixing the compound as shown in Formula IIb and the organic solvent toluene, followed by mixing with the compound as shown in Formula IVa.

[0133] In one embodiment, in the method for preparing the polymer having repeating units as shown in Formula IV, the reaction is used directly in the copolymerization reaction of the method for preparing the block copolymer III without post-treatment.

[0134] In one embodiment, the preparation method of the block copolymer III includes the following steps: the compound shown in formula IIb and the organic solvent toluene are mixed and then reacted with the compound shown in formula IVa. After the reaction is completed, no post-treatment is required. The resulting reaction solution is mixed with the alkylaluminum reagent, stirred, mixed with the compound M, and then mixed with the organic solvent of the organoboron salt to undergo a copolymerization reaction, thereby obtaining the block copolymer shown in formula III.

[0135] In one embodiment, the method for preparing the block copolymer III satisfies the following condition: R 1 Methyl; R 2 It is a methoxy group; R 4 Methyl; R 5 The alkyl aluminum is methyl; the organic solvent is toluene; the alkyl aluminum is a trimethylaluminum n-hexane solution; the organoboron salt is [Ph3C][B(C6F5)4]; the molar ratio of the alkyl aluminum to the compound shown in formula IIb is 5:1; the molar ratio of the organoboron salt to the compound shown in formula IIb is 1:1; the molar ratio of the compound shown in formula IVa to the compound M is (1-4):1; the molar ratio of the compound shown in formula IIb to the compound shown in formula IVa is 1:(100~400).

[0136] The present invention also provides a block copolymer III, which is prepared by the method described above.

[0137] The present invention also provides a block copolymer III, wherein the block copolymer as shown in Formula III may be any of the schemes described above.

[0138] In one embodiment, the block copolymer III is thermoplastic.

[0139] In one embodiment, the block polymer III is primarily composed of repeating units as shown in Formula IV and repeating units as shown in Formula A; wherein “primarily” means that the sum of the molar percentages of the repeating units as shown in Formula IV and the repeating units as shown in Formula A in the block polymer III is greater than 90%.

[0140] The present invention also provides a method for preparing block copolymer III, comprising the following steps: in an organic solvent, in the presence of a compound as shown in formula IIb, a compound as shown in formula IVa undergoes a polymerization reaction; after the polymerization reaction is completed, the reaction solution of the polymerization reaction is mixed with alkylaluminum, compound M and organoboron salt to undergo a block copolymerization reaction to obtain the block copolymer III; the block copolymer III has repeating units as shown in formula IV and repeating units as shown in formula A; ; ; in, R 1 C 1-6 alkyl; R 2 For H, C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; R 4 C 1-6 alkyl; R 5 For H or C 1-6 alkyl; Re represents scandium.

[0141] In the preparation method of the block copolymer III, R 1 R 2 R 4 R 5 The block copolymer III, the organic solvent, the alkyl aluminum, the organoboron salt, the compound shown in formula IIb, the compound shown in formula IVa, the compound M, the repeating unit shown in formula A, and the repeating unit shown in formula IV can be any of the schemes described above.

[0142] The present invention also provides a method for preparing a polymer having repeating units as shown in Formula IV, comprising the following steps: In an organic solvent, in the presence of a compound as shown in Formula IIb, a compound as shown in Formula IVa undergoes a polymerization reaction to obtain a polymer having repeating units as shown in Formula IV. ; Among them, R 4 R 5 The compound as shown in Formula IVa, the polymer having repeating units as shown in Formula IV, and the conditions of the polymerization reaction can be any of the methods for preparing the block copolymer III.

[0143] The present invention also provides a method for preparing a polymer having repeating units as shown in Formula IV, comprising the following steps: In an organic solvent, in the presence of the compound shown in Formula IIb, alkylaluminum and organoboron salt, the compound shown in Formula IVa undergoes a polymerization reaction to obtain a polymer having repeating units as shown in Formula IV. ; Among them, R 4 R 5 The alkylaluminum, the organoboron salt, the compound as shown in Formula IVa, the polymer having repeating units as shown in Formula IV, and the conditions of the polymerization reaction can be any of the methods for preparing the block copolymer III.

[0144] In one embodiment, the number-average molecular weight of the polymer having repeating units as shown in Formula IV in the polymerization reaction is 30,000-50,000 g / mol, preferably 40,000-50,000 g / mol, for example 45,400 g / mol.

[0145] In one embodiment, the polymer having repeating units as shown in Formula IV has a molecular weight distribution index of 1-1.5 in the polymerization reaction; preferably 1.05-1.15, for example 1.1.

[0146] In one embodiment, in the polymerization reaction, the polymer having repeating units as shown in Formula IV has a molar percentage of syndiotactic (rr) of 60-90%, preferably 70-80%, for example 75%.

[0147] In one embodiment, in the polymerization reaction, in the polymer having repeating units as shown in Formula IV, R 4 and R 5 The polymer having repeating units as shown in Formula IV has a number-average molecular weight of 45,400 g / mol, a molecular weight distribution index of 1.1, and a molar percentage of syndiotactic (rr) of 75%.

[0148] This invention provides a catalyst composition comprising: compound II, alkylaluminum, and an organoboron salt; wherein compound II is a compound as shown in formula IIa or a compound as shown in formula IIb; or ; in, RE is one or more of scandium (Sc), yttrium (Y), and all lanthanides; R Ar C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 3 Replacement C 6-10 Aromatic rings; R 3 Independently for C 1-6 Alkyl, -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl.

[0149] In one embodiment, the catalyst composition wherein the compound of formula IIa is any of the methods for preparing the compound of formula I as described above.

[0150] In one embodiment, the alkylaluminum in the catalyst composition is trimethylaluminum, triethylaluminum, or triisopropylaluminum, such as trimethylaluminum.

[0151] In one embodiment, the organoboron salt in the catalyst composition is an arylborate. The arylborate is preferably a tetraarylborate. The tetraarylborate is preferably [Ph3C][B(C6F5)4].

[0152] In one embodiment, the molar ratio of the alkylaluminum to compound II in the catalyst composition is (1~10):1, for example, 5:1.

[0153] In one embodiment, the molar ratio of the organoboron salt to compound II in the catalyst composition is (1~10):1, for example, 1:1.

[0154] In one embodiment, the molar ratio of compound II, the alkylaluminum and the organoboron salt in the catalyst composition is 1:(1-10):(1-10), preferably 1:5:1.

[0155] In one embodiment, the catalyst composition in which compound II is a compound as shown in formula IIb is used to prepare the block copolymer III as described above.

[0156] In one embodiment, the catalyst composition in which compound II is any of the compounds shown in formulas 1-6 is used to prepare polymer I as described above.

[0157] The present invention also provides the use of the catalyst composition described above in the preparation of polar monomer copolymers or polar monomer homopolymers.

[0158] In one embodiment, the application is the use of the catalyst composition in a method for preparing a compound as shown in Formula I as described above, preferably, the compound II is a compound as shown in Formula IIb.

[0159] In one embodiment, the application is the use of the catalyst composition in the preparation method of the block copolymer as shown in Formula III as described above, preferably, the compound II is any compound as shown in Formulas 1-6.

[0160] Terminology section

[0161] Unless otherwise specified herein, all terms and abbreviations shall have their conventional meanings as are known to those skilled in the art.

[0162] The statement "In polymer A, the molar percentage of repeating unit B is" refers to the molar percentage of repeating unit B among all repeating units in polymer A.

[0163] The expression "a group B substituted with one or more groups A" means that one or more hydrogen atoms in group B are independently replaced by group A. When multiple groups A appear simultaneously, unless otherwise specified, their definitions are independent and do not affect each other. For example, "a C6-C group substituted with three halogens..." 10 "Aromatic" refers to C6-C 10 The aryl group will be replaced by three halogens, the definitions of which are independent and do not affect each other, including but not limited to: , wait.

[0164] The "-" at the end of a group indicates that the group is attached to the rest of the molecule through that site. For example, CH3-C(=O)- refers to an acetyl group.

[0165] The term "one or more" refers to one, two, or three.

[0166] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0167] The term "alkyl" refers to a saturated monovalent hydrocarbon group that has a specified number of carbon atoms (e.g., C1-C6), is straight-chain or branched. Alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.

[0168] The term "alkoxy" refers to the group R. X -O-,R X The definition is the same as the term "alkyl". Alkoxy groups include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, etc.

[0169] The term "aromatic ring" refers to a ring having a specified number of carbon atoms (e.g., C6-C). 10 Aromatic groups are cyclic, unsaturated, monovalent hydrocarbon groups, which can be monocyclic or polycyclic (e.g., two or three). When polycyclic, adjacent monocyclic rings share two atoms and one bond, and each ring is aromatic. The aryl group is connected to the rest of the molecule through an aromatic ring. Aromatic groups include, but are not limited to, phenyl and naphthyl groups.

[0170] The reagents and raw materials used in this invention are all commercially available.

[0171] The present invention has one or more of the following positive and progressive effects: (1) The preparation method described above can efficiently catalyze the coordination anionic polymerization of polar monomers. The catalyst used has high stability and can obtain homopolymers and block copolymers with well-defined structures in high yield. (2) The catalytic system exhibits excellent regioselectivity and stereoselectivity, enabling precise control of the polymerization process; (3) This method remains stable over a wide temperature range and can achieve controlled copolymerization without strict temperature control, thus having good operational tolerance; (4) The glass transition temperature of the polymer can be effectively controlled by adjusting the substituents on the conjugated diene benzene ring or by changing the feed ratio of monomers in the copolymerization system. (5) The resulting polymer has a high glass transition temperature, and some copolymers exhibit dual glass transition behavior. Attached Figure Description

[0172] Figure 1 Gel permeation chromatography curves of homopolymer P(4-MOPI) synthesized from different catalyst precursors in experiments I-1 to I-3; Figure 2 For the polar conjugated diene monomer M in Experiment I-9 3 Schematic diagram of the glass transition temperature of homopolymers; Figure 3 The image shows the gel chromatography spectrum of the polar conjugated diene monomer 4-MOPI and the polar monomer MMA copolymer synthesized by catalyst 7 at room temperature. The blue curve represents Experiment II-1, and the green curve represents Experiment II-3. Figure 4 The image shows the gel chromatography spectrum of the polar conjugated diene monomer 4-MOPI and the polar monomer MMA copolymer synthesized by catalyst 7 at low temperature. The black curve represents Experiment II-4, and the red curve represents Experiment II-5. Figure 5 Schematic diagram of the thermal decomposition of the polar conjugated diene monomer 4-MOPI copolymer with polar monomer MMA (Experiment II-6) and the polar conjugated diene monomer homopolymer (Experiment II-7); Figure 6 The DSC spectra of the copolymer of polar conjugated diene monomer 4-MOPI and polar monomer MMA (Experiment II-6) and the homopolymer of polar conjugated diene monomer (Experiment II-7) are shown. Detailed Implementation

[0173] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0174] Example 1

[0175] 1.25 mmol of polar monomer was dissolved in 2 mL of toluene. 125 μL of 1M AlMe3 n-hexane solution was then pipetted into the polar monomer system. After stirring for 5 min, 0.025 mmol of rare earth complex was dissolved in 2 mL of toluene and added to the system. Finally, 0.025 mmol of [Ph3C][B(C6F5)4] (co-catalyst borate) was dissolved in 2 mL of toluene and added to the system. After polymerization, a few drops of 20% (v / v) hydrochloric acid-methanol solution were slowly added dropwise with stirring to quench the system. Methanol was then added until the solid completely precipitated. The liquid was decanted, yielding a white solid of 1,4-polyconjugated diene. The solid was dried in a vacuum oven at 60 °C to constant weight. The experimental results are shown in Table 1. Gel chromatography analysis showed that all spectra were single peaks (spectroscopy for experiments I-1 to I-3 is shown in Table 1). Figure 1 (As shown).

[0176] Table 1. Experimental results of homopolymerization reactions of monomers with different polarities catalyzed by different rare earth complexes.

[0177] [a] Polymerization conditions: toluene, 4 mL; rare earth complex, 25 μmol; monomer, 1.25 mmol; [Ph3C][B(C6F5)4], 25 μmol; 1 M AlMe3 n-hexane solution, 125 μL. [b] At room temperature, after dissolving in deuterated CDCl3... 1 [c] Determined by ¹H NMR. [c] Determined by GPC spectroscopy. 10 mg of polymer was weighed and dissolved in 2 ml of HPLC-grade THF, filtered through a filter tip into a 2 ml vial, and placed in a GPC autosampler. Tetrahydrofuran was used as the mobile phase at a flow rate of 1 mL / min.

[0178] The schematic diagram of the glass transition temperature of the homopolymer in Experiment I-9 is shown below. Figure 2 As shown.

[0179] Example 2 ;

[0180] Step 1: Drying the monomer and solvent

[0181] Methyl methacrylate (MMA) was mixed with CaH2 at room temperature and stirred for two days. The mixture was then distilled off under reduced pressure, degassed three times, and oxygen was removed. Finally, it was subjected to low temperature (-35°C) under anhydrous and oxygen-free conditions. o C) Save.

[0182] Monomer M 1 After passing the column, the pure component is collected.

[0183] Step 2: Solution polymerization of the copolymer

[0184] In Table 2, experiments II-1 to II-3 and II-7 were carried out according to the following feeding method.

[0185] Weigh 0.0157 g (0.02 mmol) of rare earth complex 7 (R on the ligand). 6 The dibenzylamino group (RE is Sc) or rare earth complex 3 was dissolved in a 25 mL Schlenk flask with 2 mL of toluene. Then, m × 2 mg (i.e., m × 0.02 mmol) of methyl methacrylate was weighed and added to the solution, and the reaction was allowed to proceed for t1 minutes. After the reaction was complete, 100 μL of 1M AlMe3 n-hexane solution was added. After stirring for 5 minutes, n × 3.48 mg (i.e., n × 0.02 mmol) of 4-MOPI monomer (i.e., M... 1 Add 0.0185 g (0.02 mmol) of [Ph3C][B(C6F5)4] (co-catalyst borate) to the solution, dissolve it in 2 mL of toluene, and then quickly add it to the above solution. React for t2 minutes. After the reaction is complete, slowly add ethanol dropwise with stirring until the solid completely precipitates. Pour off the liquid; the resulting methyl methacrylate and 4-MOPI monomer copolymer is a white solid. Dry in a vacuum drying oven at 60 °C to constant weight. The results are shown in Table 2. Gel chromatography analysis showed a single peak (the spectra of Experiment II-1 and Experiment II-3 are shown in Table 2). Figure 3 (As shown). The content of MMA structure was obtained by nuclear magnetic resonance hydrogen spectroscopy analysis.

[0186] In Table 2, experiments II-4 to II-6 and II-8 were carried out according to the following feeding reaction method.

[0187] Weigh 0.0157 g (0.02 mmol) of rare earth complex 7 into a 25 mL Schlenk flask, dissolve it in 2 mL of toluene, then weigh m × 2 mg (i.e., m × 0.02 mmol) of methyl methacrylate and add it to a constant pressure dropping funnel. After freezing the catalyst solution at -30 °C for 10 minutes, rapidly add the methyl methacrylate dropwise. The reaction time is t1 minutes. After the reaction is complete, transfer the reaction apparatus to a glove box and add 100 μL of 1M AlMe3 n-hexane solution. After stirring for 5 minutes, weigh n × 3.48 mg (i.e., n × 0.02 mmol) of 4-MOPI monomer and add it to the solution. Then weigh 0.0185 g (0.02 mmol) of [Ph3C][B(C6F5)4] (co-catalyst borate), dissolve it in 2 mL of toluene, and rapidly add it to the above solution. The reaction time is t2 minutes. After the reaction is complete, slowly add ethanol dropwise with stirring until the solid completely precipitates. The liquid was discarded, and the resulting methyl methacrylate and 4-MOPI monomer copolymer was a white solid. It was dried in a vacuum oven at 60 °C to constant weight. Gel chromatography analysis showed a single peak (the spectra for Experiment II-4 and Experiment II-5 are shown below). Figure 4 (As shown in the figure). The content of MMA structure was obtained by nuclear magnetic resonance hydrogen spectroscopy analysis, and the experimental results are shown in Table 2.

[0188] Table 2. Methyl methacrylate and M catalyzed by rare earth catalysts 1 Experimental results of copolymerization reaction

[0189] Among them: catalyst 7, the R group on the ligand is dibenzylamino, and the central metal is Sc; the polymer separation yield is approximately 99%. Experiments II-1 to II-3 and II-7 were synthesized at room temperature, while experiments II-4 to II-6 and II-8 were synthesized at -30 degrees Celsius. [a] Polymerization reaction conditions: 7, 20 μ mol; [7] / [borate] = 1 / 1 (mol / mol); toluene, 4 mL; 25 o C. [b] Molar ratio relative to the center of Sc. [c,d] From 1 Determined by H NMR. [e] Determined by GPC spectrum. [f] -30 o C. [g] Determined by DSC spectrum. [h] The catalyst is 3,20 μ mol.

[0190] The thermal decomposition diagrams for Experiments II-6 and II-7 are shown below. Figure 5 As shown; the DSC spectra of Experiment II-6 and Experiment II-7 are as follows. Figure 6 As shown.

[0191] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. A method for preparing block copolymer III, characterized in that, It includes the following steps: in an organic solvent, in the presence of alkylaluminum, organoboron salt and a compound as shown in Formula IIb, a polymer having a repeating unit as shown in Formula IV and compound M undergo a block copolymerization reaction to obtain block copolymer III; said block copolymer III has repeating units as shown in Formula IV and repeating units as shown in Formula A. ； ； in, R 1 is C 1-6 alkyl; R 2 H, C 1-6 alkyl, -O-C 1-6 alkyl, C 1-6 alkyl or -O-C 1-6 alkyl; R 4 is C 1-6 alkyl; R 5 is H or C 1-6 alkyl; Re represents scandium.

2. The method for preparing block copolymer III as described in claim 1, characterized in that, It meets one or more of the following conditions: (1) R 1 In particular, the C 1-6 alkyl is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl; for example methyl or i-propyl; (2) R 2 In particular, the C 1-6 alkyl is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl; for example methyl; (3) R 2 in which the -O-C 1-6 alkyl is methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy or t-butoxy; for example methoxy; (4) R 2 C1-C6-alkyl substituted by 1, 2 or 3 halogen, wherein the halogen is F, CI, Br or I, e.g. F; 1-6 C1-C6-alkyl and -O-C1-C6-alkyl substituted by 1, 2 or 3 halogen, wherein the halogen is F, CI, Br or I, e.g. F; 1-6 C1-C6-alkyl substituted by 1, 2 or 3 halogen, wherein the halogen is F, CI, Br or I, e.g. F; (5) R 2 C1-C6alkyl substituted with 1, 2, or 3 halogen; 1-6 C1-C6alkyl is trifluoromethyl; (6) R 4 In particular, the C 1-6 alkyl is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl; for example methyl; (7) R 5 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl; (8) The block copolymer III is a binary block copolymer; (9) The number average molecular weight of the block copolymer III is 1,000-100,000 g / mol, preferably 10,000-60,000 g / mol, more preferably 10,100-56,900 g / mol, for example 10,100 g / mol, 10,800 g / mol, 23,400 g / mol, 18,200 g / mol, 22,800 g / mol or 56,900 g / mol; (10) The molecular weight distribution index of the block copolymer III is 1-2, preferably 1.1-1.7, more preferably 1.5-1.7, for example 1.5, 1.6 or 1.7; (11) In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 10-90%, preferably 15-85%, for example 18.4%, 47.6%, 67.1%, 48.5%, 64.2% or 83.0%; (12) In the block copolymer III, the molar percentage of repeating units formed by 1,4-addition in the blocks derived from the compound M is 90%-100%, preferably 92-95%, more preferably 93-95%, for example 92%, 93%, 94% or 95%; (13) In the block copolymer III, the molar percentage of syndiotactic structure in the blocks having repeating units as shown in Formula IV is 70-80%, preferably 73-77%, more preferably 73-76%, for example 73%, 74%, 75%, 76% or 77%.

3. The method for preparing block copolymer III as described in claim 1, characterized in that, It meets one or more of the following conditions: (1) The repeating unit shown in Formula IV is as follows: ; (2) The compound M has the following structure: ; (3) The repeating unit shown in equation A is as follows: ; (4) The organic solvent is an aromatic hydrocarbon solvent; the aromatic hydrocarbon solvent is preferably toluene; (5) The ratio of the molar amount of the compound shown in formula IIb to the volume of the organic solvent is 0.001-0.01 mol / L, preferably 0.004-0.006, for example 0.005 mol / L; (6) The alkylaluminum is trimethylaluminum, triethylaluminum or triisopropylaluminum, for example, trimethylaluminum; (7) The molar ratio of the alkylaluminum to the compound shown in formula IIb is (1~10):1, for example 5:1; (8) The organoboron salt is an arylborate; the arylborate is preferably a tetraarylborate; the tetraarylborate is preferably [Ph3C][B(C6F5)4]; (9) The molar ratio of the organoboron salt to the compound shown in formula IIb is (1~10):1, for example 1:1; (10) The molar ratio of the compound shown in formula IIb to the compound M is 1:(10~500), preferably 1:(50~150), for example 1:100; (11) The reaction temperature of the reaction is -78-50℃, preferably -45-35℃, more preferably -45-(-15)℃ or 10-35℃, for example -30℃ or 20-30℃, more preferably -30℃; (12) The reaction comprises the following steps: mixing a compound as shown in Formula IIb, a polymer having repeating units as shown in Formula IV, an organic solvent and a mixed solution of alkyl aluminum with compound M, and then mixing with a mixed solution of the organoboron salt and the organic solvent to undergo a block copolymerization reaction to obtain a block copolymer as shown in Formula III.

4. The method for preparing block copolymer III as described in claim 1, characterized in that, The block copolymer III satisfies any of the following schemes: (1) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 10,100 g / mol and a molecular weight distribution index of 1.

6. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 18.4%. In the blocks derived from compound M, the molar percentage of repeating units formed by 1,4-addition is 93%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 75%. (2) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 10,800 g / mol and a molecular weight distribution index of 1.

6. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 47.6%. In the blocks derived from compound M, the molar percentage of repeating units formed by 1,4-addition is 92%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 74%. (3) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 23,400 g / mol and a molecular weight distribution index of 1.

7. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 67.1%. In the blocks derived from compound M, the molar percentage of repeating units formed by 1,4-addition is 94%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 77%. (4) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 18200 g / mol and a molecular weight distribution index of 1.

5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 48.5%. In the blocks derived from compound M, the molar percentage of repeating units formed by 1,4-addition is 95%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 76%. (5) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 22,800 g / mol and a molecular weight distribution index of 1.

5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 64.2%. In the blocks derived from compound M, the molar percentage of repeating units formed by 1,4-addition is 93%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 73%. (6) The repeating unit shown in equation IV is The repeating unit shown in equation A is... The block copolymer III has a number-average molecular weight of 56,900 g / mol and a molecular weight distribution index of 1.

5. In the block copolymer III, the molar percentage of the repeating unit as shown in Formula IV is 83%. In the blocks derived from the compound M, the molar percentage of repeating units formed by 1,4-addition is 94%. In the blocks having repeating units as shown in Formula IV, the molar percentage of syndiotactic units is 74%.

5. The method for preparing block copolymer III according to any one of claims 1-4, characterized in that, The method for preparing the block copolymer III further includes a method for preparing the polymer having repeating units as shown in Formula IV, comprising the following steps: In an organic solvent, in the presence of the compound shown in Formula IIb, the compound shown in Formula IVa undergoes a polymerization reaction to obtain the polymer having the repeating unit shown in Formula IV. 。 6. The method for preparing block copolymer III as described in claim 5, characterized in that, The method for preparing the polymer having repeating units as shown in Formula IV satisfies one or more of the following conditions: (1) In the polymerization reaction, the organic solvent is an aromatic hydrocarbon solvent, preferably toluene; (2) In the polymerization reaction, the molar ratio of the compound as shown in Formula IIb to the volume of the organic solvent is 0.001-0.05 mol / L, preferably 0.008-0.012 mol / L, for example 0.01 mol / L; (3) In the polymerization reaction, the molar ratio of the compound shown in formula IIb to the compound shown in formula IVa is 1:(1~1000), preferably 1:(10~500), and more preferably 1:(100~400). (4) The reaction temperature of the polymerization reaction is -78-50℃, preferably -45-35℃, more preferably -45-(-15)℃ or 10-35℃, for example -30℃ or 20-30℃; (5) The polymerization reaction includes the following steps: the compound shown in formula IIb and the organic solvent are mixed, and then the mixture is mixed with the compound shown in formula IVa; (6) The polymerization reaction is used directly in the preparation method of block copolymer III as described in any one of claims 1-4 without post-treatment.

7. A method for preparing a polymer having repeating units as shown in Formula IV, characterized in that, It includes the following steps: In an organic solvent, in the presence of a compound as shown in Formula IIb, a compound as shown in Formula IVa undergoes a polymerization reaction to obtain a polymer having repeating units as shown in Formula IV. ； Wherein, the compound as shown in Formula IVa and the conditions of the polymerization reaction are as described in claim 5 or 6; the polymer having repeating units as shown in Formula IV is as described in any one of claims 1-6.

8. A method for preparing polymer I, characterized in that, It includes the following steps: in an organic solvent, in the presence of a compound as shown in formula IIa, an organoboron salt and an alkylaluminum, compound M undergoes a polymerization reaction to obtain polymer I having repeating units as shown in formula A; in, The compound M is a compound as shown in formula Ma, and the repeating unit as shown in formula A is a repeating unit as shown in formula Aa. Alternatively, the compound M is a compound of formula Mb, and the repeating unit of formula A is a repeating unit of formula Ab. ； R 1 Independently for C 1-6 alkyl; R 2 Independently for H and C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; R Ar C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 3 Replacement C 6-10 Aromatic rings; R 3 Independently for C 1-6 Alkyl, -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl; RE is one or more of scandium, yttrium, and all lanthanides.

9. The method for preparing polymer I as described in claim 8, characterized in that, It meets one or more of the following conditions: (1) R Ar In, the C 6-10 Aromatic rings and 1, 2 or 3 R 3 Replacement C 6-10 In the aromatic ring, the C 6-10 The aromatic ring is a benzene ring; (2) R 3 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl; (3) R 3 In the context, the -OC 1-6 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy. (4) R 3 In the context, the C substituted with one, two, or three halogens 1-6 In alkyl groups, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl; (5) R 3 In the context, the C substituted with one, two, or three halogens 1-6 In the alkyl group, the halogen is F, Cl, Br or I, for example F; (6) R 3 In the context, the C substituted with one, two, or three halogens 1-6 The alkyl group is trifluoromethyl; (7) R 1 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl or isopropyl. (8) R 2 In, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl; (9) R 2 In the context, the -OC 1-6 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy. (10) R 2 In the context, the C substituted with 1, 2, or 3 halogens 1-6 Alkyl groups and -OC groups substituted with 1, 2, or 3 halogens 1-6 In the alkyl group, the halogen is F, Cl, Br or I, for example F; (11) R 2 In the context, the C substituted with 1, 2, or 3 halogens 1-6 The alkyl group is trifluoromethyl; (12) The molecular weight distribution index of polymer I is 1-2, preferably 1.2-1.8, more preferably 1.4-1.8, for example 1.76, 1.73, 1.56, 1.63, 1.71, 1.78, 1.79, 1.42, 1.45, 1.44, 1.66 or 1.6; (13) The number average molecular weight of polymer I is 5000-40000 g / mol, preferably 6000-36000 g / mol, for example 6384 g / mol, 6993 g / mol, 7059 g / mol, 9879 g / mol, 10697 g / mol, 9719 g / mol, 10049 g / mol, 10352 g / mol, 35050 g / mol, 17181 g / mol, 34116 g / mol or 22300 g / mol; (14) In the polymer I, the molar percentage of repeating units formed by 1,4-addition is 90-99%, for example 90%, 91%, 92%, 93%, 94% or 95%.

10. The method for preparing polymer I according to claim 8, characterized in that, It meets one or more of the following conditions: (1) R 3 Independently for -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl; (2) RE is scandium, yttrium, lanthanum or lutetium, for example yttrium, lanthanum or lutetium; (3) R 1 It can be methyl or isopropyl independently; (4) R 2 Independently H, -OC 1-6 Alkyl groups or C atoms substituted with 1, 2, or 3 halogens 1-6 Alkyl group; preferably H, methoxy, or trifluoromethyl; (5) The organic solvent is an aromatic hydrocarbon solvent; the aromatic hydrocarbon solvent is preferably toluene; (6) The molar volume ratio of the compound M to the organic solvent is (0.1-1) mol / L, preferably (0.1~0.5) mol / L, for example 0.21 mol / L; (7) The alkylaluminum is trimethylaluminum, triethylaluminum or triisopropylaluminum, for example, trimethylaluminum; (8) The molar ratio of the alkylaluminum to the compound shown in formula IIa is (1~10):1, for example 5:1; (9) The organoboron salt is an arylborate; the arylborate is preferably a tetraarylborate; the tetraarylborate is preferably [Ph3C][B(C6F5)4]; (10) The molar ratio of the organoboron salt to the compound shown in formula IIa is (1~10):1, for example 1:1; (11) The molar ratio of the compound shown in formula IIa to the compound M is 1:(10~100), for example 1:50 or 1:100; (12) The reaction temperature is 0-50℃, preferably 10-35℃.

11. The method for preparing polymer I as described in claim 8, characterized in that, It meets one or more of the following conditions: (1) The compound shown in formula IIa is any of the structures shown in formulas 1-6: 、 、 、 、 、 ； (2) The compound shown in formula Ma has the following structure: ； (3) The compound represented by formula Mb has any of the following structures: , , or ; (4) The repeating unit shown in equation Aa is the repeating unit shown in equation Aa-4: ； (5) The repeating unit shown in formula Ab is any repeating unit shown in formula Ab-1, Ab-2, Ab-3 or Ab-6: , , or ; Preferably, the preparation method of polymer I satisfies one or more of the following conditions: (1) In the polymer I, the repeating unit as shown in Formula A is the repeating unit as shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.76, the number average molecular weight is 6384 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 94%. (2) In the polymer I, the repeating unit shown in formula A is the repeating unit shown in formula Ab-1, the molecular weight distribution index of the polymer I is 1.73, the number average molecular weight is 6993 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 93%. (3) In the polymer I, the repeating unit shown in Formula A is the repeating unit shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.56, the number average molecular weight is 7059 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 93%. (4) In the polymer I, the repeating unit shown in formula A is the repeating unit shown in formula Ab-1, the molecular weight distribution index of the polymer I is 1.63, the number average molecular weight is 9879 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 93%. (5) In the polymer I, the repeating unit shown in Formula A is the repeating unit shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.71, the number average molecular weight is 10697 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 93%. (6) In the polymer I, the repeating unit as shown in Formula A is the repeating unit as shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.78, the number average molecular weight is 9717 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 90%. (7) In the polymer I, the repeating unit as shown in Formula A is the repeating unit as shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.79, the number average molecular weight is 10049 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 93%. (8) In the polymer I, the repeating unit shown in formula A is the repeating unit shown in formula Ab-2, the molecular weight distribution index of the polymer I is 1.42, the number average molecular weight is 10352 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 90%. (9) In the polymer I, the repeating unit as shown in Formula A is the repeating unit as shown in Formula Ab-3, the molecular weight distribution index of the polymer I is 1.45; the number average molecular weight is 35050 g / mol; and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 91%. (10) In the polymer I, the repeating unit as shown in formula A is the repeating unit as shown in formula Aa-4, the molecular weight distribution index of the polymer I is 1.44; the number average molecular weight is 17181 g / mol; and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 95%. (11) In the polymer I, the repeating unit as shown in Formula A is the repeating unit as shown in Formula Ab-6, the molecular weight distribution index of the polymer I is 1.66; the number-average molecular weight is 34116 g / mol; and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 99%. (12) In the polymer I, the repeating unit shown in Formula A is the repeating unit shown in Formula Ab-1, the molecular weight distribution index of the polymer I is 1.6, the number average molecular weight is 22300 g / mol, and the molar percentage of the repeating unit formed by 1,4-addition in the polymer I is 92%.

12. A catalyst composition, characterized in that, It consists of the following components: compound II, alkyl aluminum and organoboron salt; said compound II is a compound as shown in formula IIa or a compound as shown in formula IIb; or ; in, RE is one or more of scandium, yttrium, and all lanthanides; R Ar C 6-10 Aromatic rings may be surrounded by one, two, or three R groups. 3 Replacement C 6-10 Aromatic rings; R 3 Independently for C 1-6 Alkyl, -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl.

13. The catalyst composition according to claim 12, characterized in that, It meets one or more of the following conditions: (1) R Ar In, the C 6-10 Aromatic rings and 1, 2 or 3 R 3 Replacement C 6-10 In the aromatic ring, the C 6-10 The aromatic ring is a benzene ring; (2) R 3 In, the C 1-6 Alkyl groups and C atoms substituted with one, two, or three halogens 1-6 In alkyl groups, the C 1-6 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; for example, methyl; (3) R 3 In the context, the -OC 1-6 The alkyl group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy; for example, methoxy. (4) R 3 In the context, the C substituted with one, two, or three halogens 1-6 In the alkyl group, the halogen is F, Cl, Br or I, for example F; (5) R 3 In the context, the C substituted with one, two, or three halogens 1-6 The alkyl group is trifluoromethyl.

14. The catalyst composition according to claim 12, characterized in that, It meets one or more of the following conditions: (1) The alkylaluminum is trimethylaluminum, triethylaluminum or triisopropylaluminum, for example, trimethylaluminum; (2) The molar ratio of the alkylaluminum to compound II is (1~10):1, for example 5:1; (3) The organic boron salt is an aryl borate; the aryl borate is preferably a tetraaryl borate; the tetraaryl borate is preferably [Ph3C][B(C6F5)4]; (4) The molar ratio of the organoboron salt to compound II is (1~10):1, for example 1:1; (5) R 3 Independently for -OC 1-6 Alkyl groups or C atoms substituted with one, two, or three halogens 1-6 alkyl; (6) RE is scandium, yttrium, lanthanum or lutetium, for example yttrium, lanthanum or lutetium.

15. The catalyst composition according to claim 12, characterized in that, Compound II is any of the compounds shown in Formulas 1-6 or Formula IIb: , , , , , or ; Preferably, compound II is a compound of formula IIb, and the catalyst composition is used to prepare block copolymer III as described in any one of claims 1-6; Alternatively, compound II may be any compound as shown in formulas 1-6, and the catalyst composition may be used to prepare polymer I as described in any one of claims 8-11.

16. The use of a catalyst composition according to any one of claims 12-15 in the preparation of polar monomer copolymers or polar monomer homopolymers; Preferably, compound II is a compound of formula IIb, and the application is the application of the catalyst composition in the preparation method according to any one of claims 1-6; And / or, the compound II is any compound as shown in Formulas 1-6, and the application is the application of the catalyst composition in the preparation method as described in any one of claims 8-11.

17. A block copolymer III, characterized in that, It has repeating units as shown in Equation IV and repeating units as shown in Equation A; ； in, R 1 C 1-6 alkyl; R 2 For H, C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; R 4 C 1-6 alkyl; R 5 For H or C 1-6 alkyl; Preferably, the block copolymer III is as described in any one of claims 1-6; More preferably, the block copolymer III is prepared by the method for preparing block copolymer III as described in any one of claims 1-6.

18. A polymer I, characterized in that, It has repeating units as shown in formula Aa or repeating units as shown in formula Ab; ； R 1 Independently for C 1-6 alkyl; R 2 Independently for H and C 1-6 Alkyl, -OC 1-6 Alkyl groups, C atoms substituted with 1, 2 or 3 halogens 1-6 Alkyl groups or -OC groups substituted with one, two, or three halogens 1-6 alkyl; Preferably, the polymer I is as described in any one of claims 8-11; More preferably, the polymer I is prepared by the method of any one of claims 8-11.

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