Lithium divinyl benzene random or block functional resin based on alkyl magnesium regulation and synthesis method thereof
Through the anion polymerization method regulated by alkylmagnesium, random, block and triblock copolymerization of divinylbenzene and functionalized styrene is achieved, solving the problem of double bond crosslinking in traditional polymerization, and improving the structural controllability and functional modification capabilities of the polymer.
Patent Information
- Application Number
- CN202510946908.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-10
- Publication Date
- 2025-08-29
AI Technical Summary
Traditional double bond monomers are easily crosslinked during polymerization, making it difficult to retain a controllable number of unreacted double bonds in the polymer main chain, limiting the possibility of subsequent processing and functional expansion of the material.
Through anionic polymerization method regulated by alkylmagnesium, random copolymerization, block copolymerization and triblock copolymerization of divinylbenzene (DVB) and functionalized styrene are selectively initiated. The highly active DVB is reacted with only one double bond to form a functionalized copolymer with overhanging vinyl groups.
The structural controllability of the polymer is achieved, and the reaction sites for subsequent hydrogen reduction and epoxidation modification are provided, which improves the physical properties and functional modification possibilities of the polymer.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of functional polymer materials and relates to a lithium-based divinylbenzene random or block functionalized resin regulated by magnesium alkyls and a method for synthesizing the same. Specifically, the invention involves random copolymerization of divinylbenzene (DVB) with functionalized styrene, block copolymerization of DVB with functionalized styrene, and triblock copolymerization of DVB with functionalized styrene and a third monomer. By selectively regulating the polymerization of DVB by magnesium alkyls, copolymers with pendant vinyl groups and functionalized sites are produced. Background Art
[0002] In the field of functional polymer materials, polymers containing double bond structures have broad application value in material modification, cross-linking, and surface functionalization due to their subsequent modifiability. Traditional double bond monomers are prone to cross-linking reactions during the polymerization process, making it difficult to retain a controllable number of unreacted double bonds in the polymer backbone, limiting the possibility of subsequent processing and functional expansion. To solve the above problems, selectively initiating a polymerization reaction at one of the double bonds to achieve linear polymerization and retain the other end or side chain double bond on the polymer chain has become a research hotspot. This type of polymer not only has good structural controllability, but also provides reaction sites for subsequent chemical reactions such as hydrogenation reduction and epoxidation modification, and has important application prospects.
[0003] Divinylbenzene (DVB) is a mature polymer industrial monomer. Due to its two vinyl groups, it is often used as a crosslinking agent to significantly improve the crosslinking density of polymers. Under the regulation and control of diphenyl magnesium system, divinylbenzene can achieve narrow distribution linear homopolymerization, but the high cost and physical properties of homopolymerized divinylbenzene make it not the first choice of industrial raw materials. As a styrene derivative, how to carry out random copolymerization of divinylbenzene with styrene and other functionalized styrene derivatives to obtain various functionalized products, or to carry out block copolymerization or introduce a third monomer to carry out triblock copolymerization is the problem that the present invention intends to solve. Summary of the Invention
[0004] In response to the problems existing in the prior art, the present invention provides a lithium-based divinylbenzene random or block functionalized resin synthesis based on alkyl magnesium regulation, which is based on an anionic polymerization method. The present invention regulates industrial divinylbenzene (DVB) through alkyl magnesium regulation and performs random copolymerization and block copolymerization with other common anionic monomers such as styrene derivatives, introduces a third monomer to form a triblock copolymer, and obtains different functionalized styrene-DVB random copolymers or block polymers with different structures and pendant ethylene groups.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is:
[0006] A method for synthesizing lithium-based divinylbenzene random or block functionalized resins regulated by alkyl magnesium. The method utilizes the special structural selectivity of alkyl magnesium as a reaction regulator, allowing the highly active monomer DVB containing two double bonds to react with only one double bond, thereby serving as one of the conventional monomers for anionic linear polymerization. The method comprises the following steps:
[0007] The first step is to synthesize an alkyl magnesium regulator containing tetrahydrofuran;
[0008] Under the protection of anhydrous and oxygen-free argon, equimolar amounts of R1-Li solution and R2-Mg-X solution were added to a three-necked flask at ice-water bath temperature, and the reaction was carried out at 0°C-10°C for 12-16 hours. The diethyl ether solvent and part of the tetrahydrofuran in the reaction system were removed by cold hydrazine.
[0009] The product was transferred to a glove box protected by anhydrous and oxygen-free argon atmosphere for filtration and titration to obtain an alkyl magnesium regulator R1-Mg-R2 containing tetrahydrofuran. The reaction formula is as follows:
[0010]
[0011] The X is a halogen, including a fluoro, chloro, bromo, or iodo group. The R1 group includes a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclopropyl, cyclopentyl, allyl, phenyl, benzyl, phenethyl, 1,1-diphenylvinyl, or tert-butanol. The R2 group includes a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclopropyl, cyclopentyl, allyl, phenyl, benzyl, phenethyl, 1,1-diphenylvinyl, or tert-butanol. In particular, when R1 or R2 is a phenyl group containing a substituent R3 or R4, the substituent R3 and R4 groups include methyl, ethyl, tert-butyl, epoxy, nitro, halogen, hydroxyl or amino groups, and the two may be the same or different, and the substitution position is ortho, meta and para. The structural formula is as follows:
[0012]
[0013] Furthermore, the solvent of the R1-Li solution is an organic solvent such as diethyl ether or tetrahydrofuran, and its concentration is 0.1-10 mol / L. The solvent of the R2-Mg-X solution is tetrahydrofuran, and its concentration is 0.1-10 mol / L.
[0014] In the second step, random copolymers, diblock copolymers, and triblock copolymers are synthesized by anionic polymerization under the action of alkyl magnesium, as follows:
[0015] 2.1) Random copolymerization of DVB and functionalized styrene to form styrene-DVB random copolymers with different functionalizations;
[0016] Styrene-DVB random copolymers with different functionalizations were synthesized by anionic polymerization in the absence of water and oxygen and under argon protection: an organic solvent, an alkyl lithium, and an alkyl magnesium regulator were sequentially added to a polymerization reactor; the reaction solution in the polymerization reactor was heated to a polymerization temperature of 20°C-70°C, commercial para- / meta-divinylbenzene and functionalized styrene monomers were mixed and added to the polymerization reactor at once. After reacting for 1-16 hours, isopropanol was quickly injected into the reaction solution to terminate the polymerization, and the reaction solution was filtered and dried in a vacuum drying oven to constant weight to obtain the corresponding polymer.
[0017] 2.2) DVB is copolymerized with functionalized styrene blocks to form styrene-DVB block copolymers with different functionalizations;
[0018] Styrene-DVB block copolymers with different functionalizations were synthesized by anionic polymerization in anhydrous and oxygen-free conditions under argon protection: an organic solvent, alkyl lithium, and alkyl magnesium regulators were sequentially added to a polymerization reactor; the reaction solution in the polymerization reactor was heated to a polymerization temperature of 20°C-70°C, and commercial para- / meta-divinylbenzene and functionalized styrene monomers were added stepwise to the polymerization reactor. After reacting for 1-16 hours, isopropanol was quickly injected into the reaction solution to terminate the polymerization, and the reaction solution was filtered and dried in a vacuum drying oven to constant weight to obtain the corresponding polymer.
[0019] 2.3) copolymerizing DVB, a styrene derivative, and a third monomer by a stepwise feeding method to form triblock copolymers of styrene-DVB and a third monomer with different functionalizations;
[0020] In the absence of water and oxygen and under argon protection, triblock copolymers of different functionalized styrene-DVB and a third monomer were synthesized by anionic polymerization: an organic solvent, an alkyl lithium, and an alkyl magnesium regulator were sequentially added to a polymerization reactor; the reaction solution in the polymerization reactor was heated to a polymerization temperature of 20°C-70°C, and commercial para- / meta-divinylbenzene, functionalized styrene monomers, and the third monomer were added stepwise to the polymerization reactor. After reacting for 1-16 hours, isopropanol was quickly injected into the reaction solution to terminate the polymerization, and the reaction solution was filtered and dried in a vacuum drying oven to constant weight to obtain the corresponding polymer.
[0021] The regulator is an alkyl magnesium containing THF;
[0022] The addition amounts of the regulator and alkyl lithium are: alkyl magnesium / Li=2-8 equivalents, THF / Li=25-100 equivalents.
[0023] The organic solvent is selected from a non-polar aromatic hydrocarbon solvent or a mixture of several hydrocarbon solvents, generally selected from benzene, toluene, and ethylbenzene. A THF solvent is also introduced as a regulator, and THF / Li is 25-100 equivalents.
[0024] The alkyl lithium initiator is selected from a monofunctional alkyl lithium initiator; the monofunctional lithium initiator is any initiator or a mixture of several initiators disclosed in the prior art that can be used for anionic polymerization reactions, generally selected from: RLi, TRLi, one or a mixture of several monofunctional lithium initiators, R is a hydrocarbon group with 2-20 carbon atoms, R can be an alkane group or an aromatic hydrocarbon group, T is a metal atom or a nitrogen atom, generally a metal element such as tin Sn, silicon Si, lead Pb, titanium Ti, germanium Ge, etc., preferably selected from: ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and a monofunctional lithium initiator containing tin or nitrogen atoms.
[0025] A lithium-based divinylbenzene random or block functionalized resin regulated by alkyl magnesium is prepared by the above-mentioned synthesis method, comprising:
[0026] The functionalized styrene-DVB random copolymers have a number average molecular weight (Mn) ranging from 2,000 to 100,000 g / mol and a molecular weight distribution index (PDI) ranging from 1.11 to 2.5. The DVB content in the random copolymers is determined to be 10% to 95% by H-NMR spectroscopy.
[0027] The functionalized styrene-DVB block copolymers have a number average molecular weight (Mn) ranging from 2,000 to 100,000 g / mol and a molecular weight distribution index (PDI) ranging from 1.11 to 2.5. The DVB content in the random copolymers is determined to be 10% to 95% by H-NMR spectroscopy.
[0028] The triblock copolymers of the different functionalized styrene-DVB and the third monomer have a number average molecular weight (Mn) ranging from 2000 to 100000 g / mol and a molecular weight distribution index (PDI) ranging from 1.11 to 2.5. The DVB content in the random copolymers is 10% to 95% as determined by H-NMR spectroscopy.
[0029] Compared with divinylbenzene linear homopolymerization, the synthesis of divinylbenzene random or block functionalized resin has the following beneficial effects:
[0030] By copolymerizing with various functionalized styrene derivatives, divinylbenzene polymers can be modified with various functionalizations, which greatly enhances the physical properties of PDVB while reducing its cost, thereby obtaining different types of styrene polymers containing pendant vinyl groups and different functionalizations such as epoxy, p-tert-butyl, nitro, etc. DETAILED DESCRIPTION
[0031] The following examples are provided as further illustrations of the present invention, but are not intended to limit the scope of the present invention. The polymer structure was analyzed by nuclear magnetic resonance spectroscopy, and the molecular weight and molecular weight distribution index (PDI) of the polymer were analyzed by gel permeation chromatography.
[0032] Preparation method of embodiment regulator diphenyl magnesium:
[0033] The alkyl magnesium groups R1 and R2 are both phenyl groups. Under the protection of anhydrous and oxygen-free argon, 500 ml of 1 mol / L phenyllithium (solvent: diethyl ether) and 250 ml of 2 mol / L phenylmagnesium chloride (solvent: tetrahydrofuran) were added to a three-necked flask at ice-water bath temperature and reacted overnight. The diethyl ether solvent and part of the tetrahydrofuran in the reaction system were then removed by cold hydrazine. The product was transferred to a glove box protected by anhydrous and oxygen-free argon for filtration, titration, and other treatments.
[0034] Example Regulator 1,1-diphenylethylenephenyl magnesium preparation method:
[0035] The alkyl magnesium R1 group is 1,1-diphenylethylene, and the R2 group is phenyl. Under an anhydrous and oxygen-free argon atmosphere, 0.5 mol of 1,1-diphenylethylene lithium and 250 ml of 2 mol / L phenylmagnesium chloride (solvent: tetrahydrofuran) were added to a three-necked flask at ice-water temperature and allowed to react overnight. The tetrahydrofuran was then partially removed from the reaction system using cold hydrazine. The product was transferred to an anhydrous and oxygen-free argon glove box for filtration, titration, and other processing.
[0036] Preparation method of embodiment regulator benzylphenyl magnesium:
[0037] The alkyl magnesium R1 group is phenyl, and the R2 group is benzyl. Under the protection of anhydrous and oxygen-free argon, 500 ml of 1 mol / L phenyl lithium (solvent: diethyl ether) and 250 ml of 2 mol / L benzyl magnesium chloride (solvent: tetrahydrofuran) were added to a three-necked flask at ice-water bath temperature and reacted overnight. The diethyl ether solvent and part of the tetrahydrofuran in the reaction system were then removed by cold hydrazine. The product was transferred to a glove box protected by anhydrous and oxygen-free argon for filtration, titration, and other treatments.
[0038] The embodiments of the invention are as follows:
[0039] Example 1: Preparation of random copolymer of DVB and styrene by diphenylmagnesium regulation
[0040] In an anhydrous, oxygen-free, argon-protected glove box, 3.8 g of benzene was added to a 20 mL polymerization bottle in sequence, and the initiator sec-butyl lithium was injected according to the set molecular weight of 5 kg / mol, and then 78 μl of diphenyl magnesium (diphenyl magnesium / Li=4 equivalents, THF / Li=25 equivalents) was added. Finally, a mixture of 0.2 g of commercial DVB and 0.2 g of styrene was added. After 32 hours of reaction, isopropanol was quickly injected into the reaction solution to terminate the polymerization, filtered, and dried to constant weight in a vacuum drying oven to obtain a random copolymer of DVB and styrene. Its number average molecular weight is 4 kg / mol, and the molecular weight distribution is 1.65. The obtained polymer was characterized by nuclear magnetic hydrogen spectrum, and it was found that DVB accounted for 42%.
[0041] Example 2: Preparation of block copolymers of DVB and styrene by diphenylmagnesium regulation
[0042] In an anhydrous, oxygen-free, argon-protected glove box, 3.8 g of benzene was added to a 20 mL polymerization bottle in sequence, and the initiator sec-butyl lithium was injected according to the set molecular weight of 5 kg / mol, and then 78 μl of diphenyl magnesium (diphenyl magnesium / Li=4 equivalents, THF / Li=25 equivalents) was added, and finally 0.2 g of commercial DVB was added. After the reaction was allowed to react for 8 hours, 0.2 g of styrene was added to the polymerization reactor. After continuing the reaction for 8 hours, isopropanol was quickly injected into the reaction solution to terminate the polymerization, filtered, and dried in a vacuum drying oven to constant weight to obtain a DVB and styrene block copolymer. Its number average molecular weight is 4 kg / mol, and the molecular weight distribution is 1.71. The obtained polymer was characterized by nuclear magnetic hydrogen spectrum, and it was found that DVB accounted for 40%.
[0043] Example 3: Preparation of a triblock copolymer of DVB, styrene and isoprene by diphenylmagnesium regulation
[0044] In an anhydrous, oxygen-free, argon-protected glove box, 3.8 g of benzene was added to a 20 mL polymerization bottle in sequence, and the initiator sec-butyl lithium was injected according to the set molecular weight of 5 kg / mol, and then 78 μl of diphenyl magnesium (diphenyl magnesium / Li=4 equivalents, THF / Li=25 equivalents) was added, followed by 0.2 g of commercial DVB. After 4 hours of reaction, 0.2 g of styrene was added to the polymerization reactor. After continuing the reaction for 4 hours, 0.2 g of isoprene was added to the reaction polymerizer. After 4 hours, isopropanol was quickly injected into the reaction solution to terminate the polymerization, filtered, and dried in a vacuum drying oven to constant weight to obtain a DVB and styrene block copolymer. Its number average molecular weight was 4 kg / mol, and the molecular weight distribution was 2.01. The obtained polymer was characterized by nuclear magnetic hydrogen spectrum, and it was found that DVB accounted for 30%, styrene accounted for 35%, and isoprene accounted for 35%.
[0045] Example 4.
[0046] Compared with Example 1, all other characteristics were the same as in Example 1, except that the diphenylmagnesium / lithium equivalent ratio used was 2, the reaction temperature was 25°C, and the reaction time was 8 hours. The corresponding DVB-styrene random copolymer obtained had a molecular weight of 3000 g / mol and a PDI of 2.01.
[0047] Example 5.
[0048] Compared with Example 1, all other characteristics were the same as in Example 1, except that the diphenylmagnesium / lithium equivalent ratio used was 6, the reaction temperature was 40°C, and the reaction time was 16 hours. The corresponding DVB-styrene random copolymer obtained had a molecular weight of 3300 g / mol and a PDI of 2.12.
[0049] Example 6.
[0050] Compared with Example 1, other features are the same as those of Example 1, except that the diphenyl magnesium / lithium equivalent ratio used is 8, the reaction temperature is 70°C, and the reaction time is 8 hours. The corresponding DVB-styrene random copolymer obtained has a molecular weight of 2000 g / mol and a PDI of 1.43.
[0051] Example 8.
[0052] Compared with Example 1, all other characteristics were the same as in Example 1, except that a THF / Li equivalent of 100 was used, the reaction temperature was 25° C., and the reaction time was 16 h. The corresponding DVB-styrene random copolymer obtained had a molecular weight of 4200 g / mol and a PDI of 1.83.
[0053] Example 9.
[0054] Compared with Example 1, all other characteristics were the same as those of Example 1, except that a THF / Li equivalent of 50 was used, the reaction temperature was 25° C., and the reaction time was 16 h. The corresponding DVB-styrene random copolymer obtained had a molecular weight of 3600 g / mol and a PDI of 1.71.
[0055] Example 10.
[0056] Compared with Example 1, other features are the same as those of Example 1, except that 0.2 g of commercial DVB is added to 1.8 g of benzene, and the corresponding DVB-styrene random copolymer obtained has a molecular weight of 2800 g / mol and a PDI of 2.12.
[0057] Example 11.
[0058] Compared with Example 1, other features are the same as those of Example 1, except that 0.2 g of commercial DVB is added to 0.8 g of benzene, and the corresponding DVB-styrene random copolymer obtained has a molecular weight of 3700 g / mol and a PDI of 2.5.
[0059] Example 12.
[0060] Compared with Example 1, other features are the same as those of Example 1, except that the designed molecular weight is 120,000 g / mol, the corresponding DVB-styrene random copolymer obtained is 100,000 g / mol, and the PDI is 1.75, and a high molecular weight random copolymer is successfully prepared.
[0061] Example 13.
[0062] Compared with Example 1, other features are the same as those of Example 1, except that the regulator used is 1,1-diphenylvinylphenyl magnesium, and the corresponding DVB-styrene random copolymer obtained has a molecular weight of 3300 g / mol and a PDI of 1.77.
[0063] Example 14.
[0064] Compared with Example 1, other features are the same as those of Example 1, except that the regulator used is benzylphenyl magnesium, and the corresponding DVB-styrene random copolymer obtained has a molecular weight of 2580 g / mol and a PDI of 1.96.
[0065] Example 15.
[0066] Compared with Example 1, other features are the same as those of Example 1, except that the styrene derivative used is α-methylstyrene, and the corresponding divinylbenzene and α-methylstyrene copolymer obtained has a molecular weight of 3300 and a PDI of 1.67.
[0067] Example 16.
[0068] Compared with Example 2, other features are the same as those of Example 2, except that the regulator used is 1,1-diphenylvinylphenyl magnesium, and the corresponding DVB-styrene block copolymer obtained has a molecular weight of 3500 g / mol and a PDI of 1.87.
[0069] Example 17.
[0070] Compared with Example 2, other features are the same as those of Example 2, except that the styrene derivative used is α-methylstyrene, and the corresponding divinylbenzene and α-methylstyrene copolymer obtained has a molecular weight of 2300 and a PDI of 1.66.
[0071] Example 18.
[0072] Compared with Example 3, other features are the same as those of Example 3, except that the regulator used is 1,1-diphenylvinylphenyl magnesium, and the corresponding DVB-isoprene-styrene copolymer obtained has a molecular weight of 3500 g / mol and a PDI of 1.82.
[0073] Example 19.
[0074] Compared with Example 3, other features are the same as those of Example 3, except that the styrene derivative used is α-methylstyrene, and the corresponding DVB-isoprene-α-methylstyrene copolymer obtained has a molecular weight of 2400 g / mol and a PDI of 1.83.
[0075] The present invention successfully prepares random / block polymers having pendant vinyl groups (introduced by linear polymerization of DVB) and functionalized sites (introduced by styrene derivatives) based on the structural selectivity of alkyl magnesium that enables homopolymerization of the highly active monomer divinylbenzene. The multiple processing sites also provide a basis for subsequent processing and modification thereof.
[0076] The above-described embodiments merely express the implementation methods of the present invention, but should not be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention.
Claims
1. A method for synthesizing lithium-based divinylbenzene random or block functionalized resins regulated by alkyl magnesium, characterized in that: The synthesis method uses the structural selectivity of alkyl magnesium as a reaction regulator to make the highly active monomer DVB containing two double bonds react with only one double bond, and use it as one of the monomers for anionic linear polymerization to obtain the corresponding polymer. The following steps are involved: The first step is to synthesize an alkyl magnesium regulator containing tetrahydrofuran; Under the protection of anhydrous and oxygen-free argon, equimolar amounts of R1-Li solution and R2-Mg-X solution are added at ice-water bath temperature, reacted at 0°C-10°C for 12-16 hours, and then post-treated to obtain an alkyl magnesium regulator R1-Mg-R2 containing tetrahydrofuran; The X is a halogen; the R1 group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclopentyl group, an allyl group, a phenyl group, a benzyl group, a phenethyl group, a 1,1-diphenylvinyl group, or a tert-butanol group; the R2 group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclopentyl group, an allyl group, a phenyl group, a benzyl group, a phenethyl group, a 1,1-diphenylvinyl group, or a tert-butanol group; The solvent of the R1-Li solution is an organic solvent; the solvent of the R2-Mg-X solution is tetrahydrofuran; In the second step, random copolymers, diblock copolymers, and triblock copolymers are synthesized by anionic polymerization under the action of alkyl magnesium, as follows: Step 2.1, random copolymerization of DVB and functionalized styrene to form styrene-DVB random copolymers with different functionalizations; Step 2.2, copolymerizing DVB with functionalized styrene blocks to form styrene-DVB block copolymers with different functionalizations; In step 2.3, DVB, a styrene derivative and a third monomer are triblock copolymerized by a stepwise feeding method to form triblock copolymers of styrene-DVB and a third monomer with different functionalizations.
2. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 1, characterized in that: In the first step: Said X comprises a fluoro group, a chloro group, a bromo group or an iodo group; When R1 or R2 is a phenyl group containing a substituent R3 or R4, the substituent R3 and R4 groups include methyl, ethyl, tert-butyl, epoxy, nitro, halogen, hydroxyl or amino groups, and the two may be the same or different. The substitution position is ortho, meta and para. The structural formula is:
3. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 1, characterized in that: In the first step, the solvent of the R1-Li solution is diethyl ether or tetrahydrofuran, and the concentration of the R1-Li solution is 0.1-10 mol / L; the concentration of the R2-Mg-X solution is 0.1-10 mol / L.
4. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 1, characterized in that: The step 2.1 is specifically as follows: In anhydrous and oxygen-free environment and under argon protection, an organic solvent, an alkyl lithium and an alkyl magnesium regulator are sequentially added to a polymerization reactor; after the reaction liquid in the polymerization reactor is heated to a polymerization temperature of 20°C-70°C, para- / meta-divinylbenzene and a functionalized styrene monomer are mixed and added to the polymerization reactor at once, and after reacting for 1-16 hours, post-treatment is performed to obtain a styrene-DVB random copolymer.
5. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 1, characterized in that: The step 2.2 is specifically as follows: In anhydrous and oxygen-free environment and under argon protection, an organic solvent, an alkyl lithium, and an alkyl magnesium regulator are sequentially added to a polymerization reactor; after the reaction liquid in the polymerization reactor is heated to a polymerization temperature of 20°C-70°C, para- / meta-divinylbenzene and a functionalized styrene monomer are added stepwise to the polymerization reactor, and after reacting for 1-16 hours, post-treatment is performed to obtain a styrene-DVB block copolymer.
6. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 1, characterized in that: The step 2.3 is specifically as follows: In anhydrous and oxygen-free environment and under argon protection, an organic solvent, an alkyl lithium, and an alkyl magnesium regulator are sequentially added to a polymerization reactor; after the reaction liquid in the polymerization reactor is heated to a polymerization temperature of 20°C-70°C, para- / meta-divinylbenzene, a functionalized styrene monomer, and a third monomer are added stepwise to the polymerization reactor, and after reacting for 1-16 hours, post-treatment is performed to obtain a triblock copolymer.
7. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 4, 5 or 6, characterized in that: The post-treatment comprises injecting isopropanol into the reaction solution to terminate the polymerization, filtering, and vacuum drying the mixture to a constant weight.
8. The method for synthesizing a lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 4, 5 or 6, characterized in that: In the specific steps: The regulator is an alkyl magnesium containing THF; The addition amounts of the regulator and alkyl lithium are: alkyl magnesium / Li = 2-8 equivalents, THF / Li = 25-100 equivalents; The organic solvent is selected from a hydrocarbon solvent of non-polar aromatic hydrocarbons or a mixture of several hydrocarbon solvents; The alkyl lithium initiator is selected from monofunctional alkyl lithium initiators.
9. A lithium-based divinylbenzene random or block functionalized resin regulated by alkyl magnesium, characterized in that: Prepared by the synthesis method according to any one of claims 1 to 8, specifically: The different functionalized styrene-DVB random copolymers have a number average molecular weight Mn range of 2000-100000 g / mol and a molecular weight distribution index PDI range of 1.11-2.5; The different functionalized styrene-DVB block copolymers have a number average molecular weight Mn ranging from 2000 to 100000 g / mol and a molecular weight distribution index PDI ranging from 1.11 to 2.5; The triblock copolymer of the differently functionalized styrene-DVB and the third monomer has a number average molecular weight Mn in the range of 2000-100000 g / mol and a molecular weight distribution index PDI in the range of 1.11-2.
5.
10. The lithium-based divinylbenzene random or block functionalized resin based on alkyl magnesium regulation according to claim 9, characterized in that: The different functionalized styrene-DVB random copolymers have a DVB content of 10% to 95% as characterized by H-NMR spectroscopy; The DVB content in the random copolymers of the different functionalized styrene-DVB block copolymers is 10%-95% as characterized by H-NMR spectroscopy; The triblock copolymer of styrene-DVB with different functionalizations and a third monomer has a DVB content of 10%-95% as characterized by nuclear magnetic hydrogen spectrum.