CN-122010792-A - Preparation method of sodium methacryloyl taurate monomer, taurine-containing polymer derived from monomer, preparation method and application thereof

CN122010792ACN 122010792 ACN122010792 ACN 122010792ACN-122010792-A

Abstract

The application discloses a preparation method of a sodium methacryloyl taurate monomer, a taurine-containing polymer derived from the monomer, and a preparation method and application thereof, and belongs to the technical field of high polymer synthesis. The preparation method of the sodium methacryloyl taurate monomer comprises the steps of reacting taurine and sodium hydroxide in water, adding reaction liquid into tetrahydrofuran or 2-methyltetrahydrofuran, adding sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate to prepare suspension, adding tetrahydrofuran or 2-methyltetrahydrofuran solution of methacryloyl chloride into the suspension for contact reaction, and carrying out post-treatment separation on the reaction liquid to obtain the sodium methacryloyl taurate monomer. The preparation method realizes the breakthrough of the organic phase-solid phase reaction system to replace the aqueous phase-organic phase reaction system, effectively inhibits the hydrolysis side reaction of small molecular acyl chloride, achieves the great improvement of the yield and purity of the taurine monomer synthesized by the acyl chloride method, and lays a foundation for the industrialized application of the taurine-containing polymer.

Inventors

CHEN YUANWEI
CAO JUN
QIN LANG
LI SAI
MAO JUNHAN
YUAN BAOHUA
SU XIANG

Assignees

北京科技大学

Dates

Publication Date: 20260512
Application Date: 20260108

Claims (10)

1. A method for preparing a sodium methacryloyl taurate monomer, comprising the steps of: reacting taurine and sodium hydroxide in water, adding the reaction solution into tetrahydrofuran or 2-methyltetrahydrofuran, and then adding sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate to prepare suspension; Adding tetrahydrofuran or 2-methyltetrahydrofuran solution of methacryloyl chloride into the suspension for contact reaction, and then carrying out solid-liquid separation on the reaction solution, wherein the liquid phase is subjected to diethyl ether precipitation to obtain a precipitate A; After the sediment A and the sediment B are dissolved in methanol, diethyl ether is added for sediment, and the sediment is washed and dried in sequence, so that the sodium methacryloyl taurate monomer is obtained, and the chemical structure of the sodium methacryloyl taurate monomer is shown as the formula (i): (i)。
2. The preparation method of claim 1, wherein the molar ratio of taurine, sodium hydroxide, sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate to methacryloyl chloride is 1 (0.5-2.5): 0.7-4): 0.8-3.
3. The method according to claim 1, wherein the sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate is at least one selected from the group consisting of disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen carbonate and potassium hydrogen carbonate.
4. The preparation method according to claim 1, wherein when the tetrahydrofuran or 2-methyltetrahydrofuran solution of methacryloyl chloride is added to the suspension for contact reaction, the addition rate is 1-1.5 mL/min, and the molar amount of the tetrahydrofuran or 2-methyltetrahydrofuran solution of methacryloyl chloride is 1.1mol/30mL.
5. A taurine-containing polymer characterized by comprising polymethacryloyl taurine and a methacryloyl taurine-methacrylic acid copolymer; the sodium methacryloyl taurate monomer prepared by the preparation method of any one of claims 1-4 is prepared by self-polymerization of the polymethacrylyl taurate; the chemical structure of the polymethacrylyl taurine is shown as a formula (ii) or (iii); (ii) (iii) Wherein n 1 is 10-50, n 2 is 400-4000; the methacrylic taurine-methacrylic acid copolymer is prepared by copolymerizing a sodium methacryloyl taurine monomer and a methacrylic acid monomer prepared by the preparation method of any one of claims 1-4; The chemical structure of the methacryloyl taurine-methacrylic acid copolymer is shown as a formula (iv) or (v); (iv) (v) Wherein n is 400-4000, and m is 400-4000.
6. A method of preparing the taurine-containing polymer of claim 5 by RAFT controlled polymerization, comprising: Dissolving a monomer, an azo RAFT reagent and a dithiobenzoate RAFT initiator in a mixed solution of methanol/water, carrying out RAFT polymerization reaction in a nitrogen atmosphere after freezing, evacuating and melting, precipitating a product solution by tetrahydrofuran after the reaction is finished, collecting a precipitate and dissolving the precipitate by methanol, precipitating by tetrahydrofuran again, collecting the precipitate, and finally washing and drying the precipitate in sequence to obtain the taurine polymer; wherein the monomer is the sodium methacryloyl taurate monomer or a mixture of the sodium methacryloyl taurate monomer and methacrylic acid monomer with sodium hydroxide; When the monomer is sodium methacryloyl taurate monomer, the obtained taurine polymer is polymethacrylyl taurate shown in a chemical structure (ii), and when the monomer is sodium methacryloyl taurate monomer and a mixture of methacrylic acid monomer and sodium hydroxide, the obtained taurine polymer is methacrylic acid-methacrylic acid copolymer shown in a chemical structure (iv).
7. The method of claim 6, wherein the RAFT polymerization reaction is carried out at a temperature of 70-75 ℃ for a time of 24-48 hours; and/or the molar ratio of the azo RAFT agent to the dithiobenzoate RAFT initiator is 1:5; And/or when the monomer is sodium methacryloyl taurate monomer, the molar ratio of the sodium methacryloyl taurate monomer to the dithiobenzoate RAFT initiator is n 1 /n 2 :1, and the mass fraction of the sodium methacryloyl taurate monomer is 10-25wt% of the mixed solution; And/or, when the monomer is a mixture of sodium methacrylate and methacrylic acid monomer, the molar ratio of sodium hydroxide to methacrylic acid monomer is 0.5:1, and the molar ratio of the total mole number of the sodium methacrylate and methacrylic acid monomer to the dithiobenzoate RAFT initiator is (n+m): 1.
8. A method of preparing the taurine polymer of claim 4 by a sulfate initiated polymerization process, comprising: Dissolving a monomer and a persulfate initiator in a mixed solution dissolved in methanol/water, carrying out persulfate initiation polymerization reaction in a nitrogen atmosphere, precipitating a product solution by tetrahydrofuran, collecting a precipitate, dissolving the precipitate by methanol, precipitating by tetrahydrofuran again, collecting the precipitate, and finally washing and drying the precipitate in sequence to obtain the taurine polymer; Wherein the monomer is sodium methacryloyl taurate monomer or a mixture of sodium methacryloyl taurate monomer and methacrylic acid monomer and sodium hydroxide; When the monomer is sodium methacryloyl taurate monomer, the obtained taurine polymer is polymethacrylyl taurate shown in chemical structure (iii), and when the monomer is sodium methacryloyl taurate monomer and a mixture of methacrylic acid monomer and sodium hydroxide, the obtained taurine polymer is methacrylic acid-methacrylic acid copolymer shown in chemical structure (v).
9. The method of claim 8, wherein the persulfate is initiated at a temperature of 70-75 ℃ for a time of 24-48 hours; And/or the persulfate initiator is one of K 2 S 2 O 8 、Na 2 S 2 O 8 or (NH 4 ) 2 S 2 O 8 ; And/or when the monomer is sodium methacryloyl taurate monomer, the mass ratio of the sodium methacryloyl taurate to the persulfate initiator is 100:0.2-2, and the mass fraction of the sodium methacryloyl taurate monomer is 10-25wt% of the mixed solution; And/or when the monomers are sodium methacryloyl taurate monomers and a mixture of methacrylic acid monomers and sodium hydroxide, the molar ratio of the sodium hydroxide to the methacrylic acid monomers is 0.5:1, and the mass ratio of the total mass of the sodium methacryloyl taurate monomers and the methacrylic acid monomers to the persulfate initiator is 100:0.2-2.
10. Use of the taurine-containing polymer of claim 4 in biomedical materials, cosmetic care materials, sensors, water treatment materials, and anti-fouling coating materials.

Description

Preparation method of sodium methacryloyl taurate monomer, taurine-containing polymer derived from monomer, preparation method and application thereof Technical Field The application belongs to the technical field of high polymer synthesis, and particularly relates to a preparation method of a sodium methacryloyl taurate monomer, a taurine-containing polymer derived from the monomer, and a preparation method and application thereof. Background The taurine derivative polymer is widely applied to various fields of biomedical use, membrane modification, chromatographic separation and the like due to good biocompatibility, hydrophilicity and ionization capability. However, the traditional preparation of the taurine-containing polymer is mainly based on polymer grafting modification, and the problems of low grafting rate, poor controllability, high cost, large pollution and the like generally exist, so that the large-scale preparation difficulty is high, and the application conversion of the taurine-containing polymer is greatly limited. Therefore, the preparation method of copolymerization of taurine unsaturated monomers becomes a research hot spot in the preparation field of taurine-containing polymers. At present, an acyl chloride method is one of the most effective strategies for constructing taurine monomers, and is characterized in that functional monomers are prepared by the reaction of acyl chloride and taurine, and then taurine-containing polymers are synthesized by means of free radical polymerization and the like. For example, christopher P.Palmer et al reacted 10-undecylenoyl chloride with taurine to produce 10-undecylenoyl taurine monomer, which was then free-radically polymerized to produce the corresponding taurine-containing polymer. However, the prior acyl chloride method for synthesizing taurine monomer has the key problems of low yield generally, namely, the taurine is only dissolved in water, the micromolecular acyl chloride is easy to hydrolyze, the aqueous phase-organic phase two-phase reaction is needed, the micromolecular acyl chloride is rapidly hydrolyzed at the interface of the aqueous phase to reduce the utilization rate, the taurine group has obvious acidity, the self amino group is easily protonated to lose nucleophilic activity, the amino group needs to be activated by adding alkali, and the alkaline environment further aggravates the hydrolysis of the micromolecular acyl chloride, so that the yield of the taurine monomer synthesized by the acyl chloride method is generally low (15-20%) due to the factors. Disclosure of Invention The application discloses a preparation method of a sodium methacryloyl taurine monomer, a taurine-containing polymer derived from the monomer, and a preparation method and application thereof, and effectively solves the technical problem of low yield of the taurine monomer synthesized by the existing acyl chloride method. In order to achieve the above purpose, the technical scheme provided by the application is as follows: in the 1 st aspect of the application, a preparation method of sodium methacryloyl taurine monomer is provided, which comprises the following steps: reacting taurine and sodium hydroxide in water, adding the reaction solution into tetrahydrofuran or 2-methyltetrahydrofuran, and then adding sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate to prepare suspension; Adding tetrahydrofuran or 2-methyltetrahydrofuran solution of methacryloyl chloride into the suspension for contact reaction, and then carrying out solid-liquid separation on the reaction solution, wherein the liquid phase is subjected to diethyl ether precipitation to obtain a precipitate A; After the sediment A and the sediment B are dissolved in methanol, diethyl ether is added for sediment, and the sediment is washed and dried in sequence, thus obtaining the sodium methacryloyl taurate monomer with the chemical structure of formula # ) The following is shown: ()。 According to the disclosure of the 1 st aspect, the mol ratio of the taurine, the sodium hydroxide, the sodium salt/potassium salt containing hydrogen phosphate or hydrogen carbonate to the methacryloyl chloride is 1 (0.5-2.5): 0.7-4): 0.8-3. According to the disclosure of the 1 st aspect, the sodium/potassium salt containing hydrogen phosphate or hydrogen carbonate is selected from at least one of disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate and potassium bicarbonate. According to the disclosure of the 1 st aspect, when the tetrahydrofuran or the 2-methyltetrahydrofuran solution of the methacryloyl chloride is added into the suspension for contact reaction, the adding rate is 1-1.5 mL/min, wherein the molar quantity of the tetrahydrofuran or the 2-methyltetrahydrofuran solution of the methacryloyl chloride is 1.1mol/30mL. Also disclosed in aspect 2 of the application is a taurine-containing polymer derived based on the sodium methacryloyl taurate monome