High-grafting density cyclic comb shaped polymer and preparation method therefor

Patent metadata

Field	Value
Publication number	US-2021122883-A1
Application number	US-202117140550-A
Country	US
Kind code	A1
Filing date	Jan 4, 2021
Priority date	Jul 4, 2018
Publication date	Apr 29, 2021
Grant date	—

Abstract

A high-grafting density cyclic comb shaped polymer and its preparation method therefor. The method comprises the following steps: 1) synthesizing linear poly(pentafluorophenyl 4-vinylbenzoate) (l-PPF4VB4.0k); 2) performing photo-induced cyclization on the linear polymer to prepare the cyclic polymer (c-PPF4VB4.0k); 3) performing post modification on the cyclic polymer c-PPF4VB4.0k by using small molecules to prepare a functionalized cyclic polymer (c-P1); 4) then performing polymer post modification on the cyclic polymer (c-P1) by using an efficient click reaction to construct the high-grafting density cyclic comb shaped polymer (c-P1-g-PS); and 5) directly performing polymer post modification on the cyclic polymer c-PPF4VB4.0k by using macromolecules to construct a high-grafting density cyclic comb shaped polymer (c-PPF4VB4.0k-g-PEG), the obtained cyclic comb shaped polymer still remaining the characteristic of a narrow molecular weight distribution.

First claim

1 . A method of preparing a high-grafting density cyclic comb shaped polymer, comprising the following steps:
(1) preparing a linear polyformate from a formate monomer as a starting material in a first solvent, in the presence of a RAFT reagent; (2) converting the linear polyformate to a cyclic polyformate through a light-induced reaction under an inert gas atmosphere and in a second solvent; (3) reacting the cyclic polyformate with a small molecule amine to obtain a functional cyclic polymer under the inert gas atmosphere and in a third solvent; and (4) reacting the functional cyclic polymer with a linear azide polystyrene to obtain the high-grafting density cyclic comb-shaped polymer in the present of pentamethyldiethylenetriamine, copper, and a copper salt, under the inert gas atmosphere and in a fourth solvent.

2 . A method of preparing a high-grafting density cyclic comb shaped polymer, comprising the following steps:
(1) preparing a linear polyformate from a formate monomer as a starting material in a first solvent, in the presence of a RAFT reagent; (2) converting the linear polyformate to a cyclic polyformate through a light-induced reaction under an inert gas atmosphere and in a second solvent; and (3) reacting the cyclic polyformate with an amino-terminated polymer to obtain the high-grafting density cyclic comb-shaped polymer under the inert gas atmosphere and in a third solvent.

3 . The method according to claim 1 , wherein in step (1), a molar ratio of the formate monomer to the RAFT reagent is (50 to 150):(1 to 2); the formate monomer is pentafluorophenyl 4-vinylphenylformate; the first solvent is toluene; a reaction temperature is 80 to 120° C., and a reaction time is 4 to 10 hours.

4 . The method according to claim 1 , wherein in step (2), the light-induced reaction is an UV irradiation reaction for 6 to 24 hours, and an UV irradiation is generated from a low pressure mercury lamp mercury lamp, a medium pressure mercury lamp, or a high pressure mercury lamp, preferably the low-pressure mercury lamp; and the second solvent is dichloromethane or acetonitrile, and a volume ratio of dichloromethane and acetonitrile is (0 to 1):(2 to 4).

5 . The method according to claim 1 , wherein 2,3-dimethylanisole, copper sulfate pentahydrate and potassium persulfate, as starting materials, are stirred in a mixed solvent of acetonitrile and water to prepare 2-methoxy-6-methylbenzaldehyde; aluminum trichloride is added to a dimethoxymethane solution of 2-methoxy-6-methylbenzaldehyde, and stirred at room temperature overnight to obtain 2-hydroxy-6-methylbenzaldehyde; 2-hydroxy-6-methylbenzaldehyde and bromopropanol are added into a solution of potassium carbonate in N,N-dimethylformamide at 90° C. overnight, after a reaction is completed, insoluble matter is removed by filtration, and HCl is added to a filtrate to obtain 2-(3-hydroxypropoxy)-6-methylbenzaldehyde; 2-(3-hydroxypropoxy)-6-methylbenzaldehyde and 4-cyano-4-(thioben-zoylthio) valeric acid are dissolved in dichloromethane, a solution of N,N′-dicyclohexylcarbimide and 4-dimethylaminopyridine in dichloromethane is added dropwise, and a resulting reaction mixture is stirred at room temperature for 24 hours to obtain the RAFT reagent.

6 . The method according to claim 1 , wherein in step (3), the solvent is tetrahydrofuran, chloroform, or dichloromethane; a molar ratio of the cyclic polyformate to the small molecule amine was (1 to 2):(40 to 80); the reaction is stirred at room temperature for 6 to 24 hours; and the small molecule amine is propargylamine.

7 . The method according to claim 1 , wherein in step (4), a molar ratio of the functional cyclic polymer, the linear azide polystyrene, pentamethyldiethylenetriamine, the copper, and the copper salt was from (1 to 2):(20 to 40):(20 to 40):(10 to 20):(20 to 40); the fourth solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide, a volume ratio of tetrahydrofuran and N,N-dimethylformamide is (2 to 4):(1 to 2); and the copper salt is cuprous bromide.

8 . The method according to claim 1 , wherein styrene, ethyl 2-bromoisobutyrate, CuBr 2 , pentamethyldiethylenetriamine, ascorbic acid, and anisole, are stirred at 90° C. for 2.5 hours to obtain a polymer; the polymer, sodium azide and N,N-dimethylformamide are mixed and stirred at room temperature for 24 hours to obtain the linear azide polystyrene.

9 . The method according to claim 2 , wherein a molar ratio of cyclic polyformate and the amino-terminated polymer is (1 to 2):(10 to 30); and the third solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide, a volume ratio of tetrahydrofuran to N,N-dimethylformamide is from (1 to 2):(1 to 2); and the amino-terminated polymer is methoxypolyethylene glycol amine.

10 . A high-grafting density cyclic comb shaped polymer with the preparation method according to claim 1 .

11 . The method according to claim 2 , wherein in step (1), a molar ratio of the formate monomer to the RAFT reagent is (50 to 150):(1 to 2); the formate monomer is pentafluorophenyl 4-vinylphenylformate; the first solvent is toluene; a reaction temperature is 80 to 120° C., and a reaction time is 4 to 10 hours.

12 . The method according to claim 2 , wherein in step (2), the light-induced reaction is an UV irradiation reaction for 6 to 24 hours, and an UV irradiation is generated from a low pressure mercury lamp mercury lamp, a medium pressure mercury lamp, or a high pressure mercury lamp, preferably the low-pressure mercury lamp; and the second solvent is dichloromethane or acetonitrile, and a volume ratio of dichloromethane and acetonitrile is (0 to 1):(2 to 4).

13 . The method according to claim 2 , wherein 2,3-dimethylanisole, copper sulfate pentahydrate and potassium persulfate, as starting materials, are stirred in a mixed solvent of acetonitrile and water to prepare 2-methoxy-6-methylbenzaldehyde; aluminum trichloride is added to a dimethoxymethane solution of 2-methoxy-6-methylbenzaldehyde, and stirred at room temperature overnight to obtain 2-hydroxy-6-methylbenzaldehyde; 2-hydroxy-6-methylbenzaldehyde and bromopropanol are added into a solution of potassium carbonate in N,N-dimethylformamide at 90° C. overnight, after a reaction is completed, insoluble matter is removed by filtration, and HCl is added to a filtrate to obtain 2-(3-hydroxypropoxy)-6-methylbenzaldehyde; 2-(3-hydroxypropoxy)-6-methylbenzaldehyde and 4-cyano-4-(thioben-zoylthio) valeric acid are dissolved in dichloromethane, a solution of N,N′-dicyclohexylcarbimide and 4-dimethylaminopyridine in dichloromethane is added dropwise, and a resulting reaction mixture is stirred at room temperature for 24 hours to obtain the RAFT reagent.

14 . A high-grafting density cyclic comb shaped polymer with the preparation method according to claim 2 .

Assignees

• Univ Soochow

Inventors

• Zhang Wei
• Zhang Shuangshuang
• Li Jieai
• Zhu Xiulin
• Zhang Zhengbiao
• Zhou Nianchen

Classifications

• C08G81/00 Primary

  Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) · CPC title

• C08G81/024 Primary

  Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G · CPC title