CN106750008A - The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel - Google Patents

Abstract

The invention relates to a preparation method of an organic amphoteric copolymer interpenetrating network gel. The method is to use methacryloyloxyethyltrimethylammonium chloride, methacrylateoxyethyl trimellitic anhydride, crotonic acid as comonomer, polyethylene glycol dimethacrylate as crosslinking agent, persulfuric acid Potassium-sodium bisulfite is used as initiator to carry out copolymerization reaction in deionized water to obtain the first network gel of organic amphoteric copolymer polymer; , triethanolamine trimethacrylate and deionized water to swell in the aqueous solution, monomers and crosslinking agents in the aqueous solution undergo copolymerization and esterification reactions through the action of potassium sulfate and pyridoxine hydrochloride, and finally obtain Organic amphoteric copolymer interpenetrating network gel.

Description

Preparation method of organic amphoteric copolymer interpenetrating network gel

technical field

The invention relates to a preparation method of an organic amphoteric copolymer interpenetrating network gel.

Background technique

Gel is a special dispersion system. Polymer molecules or colloidal particles are connected to form a three-dimensional space network structure, which can absorb a large amount of water swelling and is insoluble in water. It can maintain a certain shape in water and has both solid and liquid properties. nature. Macroscopically, polymer gel has a certain shape, which will be deformed when a certain external force is applied, and will return to its original shape after removing the external force, with solid viscoelasticity; microscopically, polymer gel has a three-dimensional network structure and is insoluble in water, three-dimensional Network molecules can be stretched in water and have liquid properties. The gel with softness, high water content and rubber viscoelasticity has been widely used in many fields such as environmental protection, textiles, building materials, petrochemicals, food, agriculture, forestry and gardening, and daily cosmetics.

Organisms including humans are composed of polymer gels, most of which are charged, such as proteins and amino acids. Copolymerized amphiphilic polymer interpenetrating network gels can obtain ever-changing specific properties with the change of copolymerization components, especially the similarity of high water content and electrical properties in the molecule to the structure of the human body, good biocompatibility, and environmental stimulus response It has some applications in the fields of drug controlled release, biosensing, tissue engineering and so on in the field of biomedicine.

At present, the main problem in the preparation method of organic amphoteric copolymerized polymer interpenetrating network gel is that the monomer acrylamide is a highly toxic drug that is "carcinogenic, distorting, and mutagenic", and the cross-linking agent N, N methylenebisacrylamide It is highly toxic and has adverse toxic effects on the gel; the interpenetrating network gel formed by a single cross-linking agent has low stability. Develop organic amphoteric copolymerized polymer interpenetrating network gels that use non-toxic or low-toxic monomers and cross-linking agents for copolymerization to reduce gel toxicity, and use compound cross-linking agents to form multiple interpenetrating networks to improve gel stability The preparation method has great practical value.

Contents of the invention

Aiming at the problems existing in the current preparation method of organic amphoteric copolymerized polymer interpenetrating network gel, the purpose of the present invention is to provide a method of copolymerizing non-toxic or low-toxic monomers and cross-linking agents to reduce the toxicity of the gel. A method for preparing an organic amphoteric copolymerized polymer interpenetrating network gel with a cross-linking agent to form multiple interpenetrating networks to improve gel stability, which is characterized in that component A and deionized water are added to a sealable reactor and stirred to prepare an aqueous solution. Control the weight concentration of component A to 28% to 62%; after the solution is prepared, evacuate to a relative vacuum of -0.02MPa to -0.08MPa, inject nitrogen to restore the reactor to normal pressure, and add the The aqueous solution prepared by component B and deionized water, the weight concentration of component B is 20%~40%; The aqueous solution prepared with deionized water, the weight concentration of component C is 5% to 15%; the pH value is controlled to 4 to 10, and the temperature is kept at 35°C to 50°C, and the stirring reaction is continued for 2h to 3.5h to obtain an organic amphoteric copolymer polymer The first network gel; then cooling, under feeding nitrogen, this first network gel is dropped into the sealable reactor that the aqueous solution that D component and deionized water are prepared is swollen, the weight concentration of D component 1.8%~11%, by weight, the weight ratio of the first network gel:D component deionized water solution=1:(95~155), swelling for 2h~6h; then add E component and deionized water The prepared aqueous solution continues to swell, the weight concentration of component E is 10% to 20%, and the swelling time is 16 h to 24 h; Keep the temperature at 95°C and react for 4h to 6h to obtain organic amphoteric copolymer interpenetrating network gel. The A component is composed of methacryloyloxyethyltrimethyl ammonium chloride, methacrylic acidoxyethyl trimellitic anhydride, and crotonic acid. Ammonium chloride: Oxyethyl trimellitic anhydride methacrylate: The ratio of the amount of crotonic acid = (0.5 ~ 1.2): (0.3 ~ 1.6): (0.4 ~ 1.1); B component is polyethylene dimethacrylate Alcohol ester, the number-average molecular weight is 2000-20000, and the total weight of the feed is 2.5%-11% of the total weight of the A component; the C component is composed of potassium persulfate-sodium bisulfite, and the total feed weight is the A component 0.3% to 1.8% of the total weight, by weight, potassium persulfate: sodium bisulfite weight ratio = 1: (0.2 to 1.1); D component consists of abscisic acid, mannitol, methacrylate oxypropyl Composition of trimellitic anhydride ester and triethanolamine trimethacrylate, based on the amount of substance, the ratio of abscisic acid: mannitol: oxypropyl methacrylate trimellitic anhydride ester=(0.5～2.0):(0.08～0.32) : (0.4～1.1), by weight, the feed weight of triethanolamine trimethacrylate is 1.8%～5.5% of the total weight of the three monomers of abscisic acid, mannitol and methacrylateoxypropyl trimellitic anhydride; Group E The component is composed of potassium persulfate and pyridoxine hydrochloride, the feeding weight of potassium persulfate is 0.1%~1.2% of the total weight of component D, and the feeding weight of pyridoxine hydrochloride is 0.8%~ 5.6%.

The technical method of the present invention is realized like this: prepare methacryloyloxyethyltrimethylammonium chloride CH ₂ =C(CH ₃ )COO(CH ₂ ) ₂ N(CH ₃ ) ₃ in a sealable reactor Cl, oxyethyl methacrylate trimellitic anhydride CH ₂ =C(CH ₃ )COO(CH ₂ ) ₂ OOCC ₆ H ₃ C ₂ O ₃ , crotonic acid CH ₃ CH=CHCOOH comonomer aqueous solution; vacuum deoxygenation Afterwards, pass through nitrogen protection, add the aqueous solution of cross-linking agent polyethylene glycol dimethacrylate; after heating up, add redox initiator potassium persulfate-sodium bisulfite K ₂ S ₂ O ₈ -NaHSO ₃ Aqueous solution, through the initiation and copolymerization chain growth reaction, the crosslinking agent polyethylene glycol dimethacrylate participates in the copolymerization reaction and the linear copolymerization macromolecule crosslinking reaction to form a crosslinking network structure, and through the chain termination reaction, organic amphoteric Copolymer first network gel. Under the protection of nitrogen gas, the first network gel of organic amphoteric copolymer polymer was prepared in abscisic acid (C ₉ H ₁₃ O ₂ )-CH=CHC(CH ₃ )=CHCOOH, mannitol HOCH ₂ (CHOH) ₄ CH ₂ OH, methyl Oxypropyl trimellitic anhydride CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ OOCC ₆ H ₃ C ₂ O ₃ , Triethanolamine trimethacrylate (CH ₂ =C(CH ₃ )COOC ₂ H ₄ ) Swell under the action of ₃ N aqueous solution, then add initiator potassium persulfate K ₂ S ₂ O ₈ , catalyst pyridoxine hydrochloride (CH ₃ )(HOCH ₂ ) ₂ (HO)C ₅ HN·HCl aqueous solution Continue to swell. During the swelling process, the monomers, crosslinking agents, initiators, and catalysts in the aqueous solution enter into the first network gel of the organic amphoteric copolymer and distribute evenly; Macromolecules, cross-linking agent triethanolamine trimethacrylate participate in the copolymerization reaction and cross-linking reaction of linear copolymer macromolecules to form a cross-linked network structure, pyridoxine hydrochloride catalyzes molecules with carboxyl groups and molecules with hydroxyl groups The molecules of the group undergo an esterification reaction. Since mannitol has six OH groups, it will form a cross-linked network structure with molecules with carboxyl groups; further reactions, and finally due to the chain termination and esterification of free radical copolymerization macromolecules The completion of organic amphoteric copolymer polymer interpenetrating network gel.

Compared with the prior art method, the outstanding advantage of the present invention is that the monomer methacryloyloxyethyl trimethyl ammonium chloride, methacrylic acid oxyethyl trimellitic anhydride ester, crotonic acid, methacrylic acid oxypropyl ammonium chloride used in the preparation technology Trimellitic anhydride ester and cross-linking agent triethanolamine trimethacrylate have low toxicity, and monomeric abscisic acid and cross-linking agent polyethylene glycol dimethacrylate and mannitol are nontoxic, which reduces the gel toxicity; the prepared interpenetrating The network gel has free radical cross-linking and esterification cross-linking network structure, which improves the stability of the interpenetrating network gel; the preparation method is simple, the reaction conditions are mild, and it is suitable for production, and has good environmental and economic benefits.

detailed description

Example 1: 124.5g of methacryloyloxyethyltrimethylammonium chloride, 110.5g of methacrylateoxyethyl trimellitic anhydride, 43g of crotonic acid and 648.8ml of deionized water are added to a sealable reactor with a volume of 2L Stir and mix evenly in the medium, the weight concentration of the aqueous solution is 30%; evacuate to a relative vacuum degree of -0.03MPa, then feed nitrogen to restore the reactor to normal pressure, add 8.3g of dimethacrylic acid with a number average molecular weight of 4000 Ethylene glycol ester and 31.4ml of deionized water prepared aqueous solution, the weight concentration of the aqueous solution is 21%; Aqueous solution, the weight concentration of the aqueous solution is 5.5%, at a constant temperature of 37 ° C, the pH value is controlled to 4.5, and the stirring reaction is continued for 2.3 hours to obtain the first network gel of the organic amphoteric copolymer polymer; then cooled, and under the nitrogen gas, 164.2g of the first network gel of organic amphoteric copolymerized polymer is put into a sealable reactor with a volume of 20L to swell, and 158.6g of abscisic acid, 18.2g of mannitol, and 145.1g of oxypropyl trimellitic anhydride methacrylate are housed in the reactor , 6.4g triethanolamine trimethacrylate and 16090.8ml deionized water prepared aqueous solution, the weight concentration of the aqueous solution is 2%, the weight of the first network gel (164.2g): the weight of the aqueous solution (16419.1g) = 1:100, swelling for 3 hours; then add 0.66g potassium persulfate, 3.28g pyridoxine hydrochloride and 33.6ml deionized water to prepare the aqueous solution to continue swelling, the weight concentration of the aqueous solution is 10.5%, swelling for 17h; after swelling is completed Raise the temperature to 77°C, control the pH value to 3.4, and react at a constant temperature of 77°C for 4.3 hours to obtain an organic amphoteric copolymer interpenetrating network gel. The gel is insoluble in water and can swell in water. The gel swelling rate (ESR) = 5267% (deionized water), and the gel swelling rate (ESR) = 5198% (1% NaCl aqueous solution by weight).

Example 2: 228.3g methacryloyloxyethyltrimethylammonium chloride, 414.4g methacrylateoxyethyl trimellitic anhydride, 86.1g crotonic acid and 485.8ml deionized water are added into a 1L sealable reactor Stir and mix evenly in the medium, the weight concentration of the aqueous solution is 60%; evacuate to a relative vacuum degree of -0.07MPa, then feed nitrogen to restore the reactor to normal pressure, add 72.9g of dimethacrylic acid with a number average molecular weight of 19000 An aqueous solution prepared from ethylene glycol ester and 114ml deionized water, the weight concentration of the aqueous solution is 39%; then the temperature is raised to 48°C, and the aqueous solution prepared from 5.47g potassium persulfate, 5.47g sodium bisulfite and 64.5ml deionized water is added , the weight concentration of the aqueous solution is 14.5%, at a constant temperature of 48 ° C, the pH value is controlled to 9.5, and the stirring reaction is continued for 3.2 hours to obtain the first network gel of the organic amphoteric copolymer polymer; then cooled, and under the nitrogen gas, the organic 57.5g of the first network gel of the amphoteric copolymer polymer is dropped into a 10L sealable reactor for swelling, and the reactor is equipped with 475.8g of abscisic acid, 54.7g of mannitol, 290.3g of methacrylate oxypropyl trimellitic anhydride, 41g of trimethyl The aqueous solution prepared by triethanolamine acrylate and 7755.6ml deionized water, the weight concentration of the aqueous solution is 10%, the weight of the first network gel (57.5g): the weight of the aqueous solution (8617.3g)=1:150, swelling 5.5 h; add 1.72g potassium persulfate, 8.62g pyridoxine hydrochloride and 42.7ml deionized water to prepare the aqueous solution to continue swelling, the weight concentration of the aqueous solution is 19.5%, swelling for 23h; after the swelling is completed, the temperature is raised to 93°C, Control the pH value to 6.5, and react at a constant temperature of 93° C. for 5.6 hours to obtain an organic amphoteric copolymer interpenetrating network gel. The gel is insoluble in water and can swell in water. The gel swelling rate (ESR) = 4275% (deionized water), and the gel swelling rate (ESR) = 4167% (1% NaCl aqueous solution by weight).

Claims (1)

1. a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel, it is characterized in that can in closed reactor plus Enter component A and deionized water stirring prepares the aqueous solution, it is 28%~62% to control the weight concentration of component A, after the completion of prepared by solution, Relative degree of vacuum is evacuated to for -0.02MPa~-0.08MPa, after being passed through nitrogen recovery reactor to normal pressure, is added under agitation Enter the aqueous solution prepared by B component and deionized water, the weight concentration of B component is 20%~40%, the aqueous solution charging knot of B component Shu Hou, is warming up to 35 DEG C~50 DEG C, and the aqueous solution prepared by component C and deionized water is added under agitation, and the weight of component C is dense It is 5%~15% to spend, and control ph is 4~10, in 35 DEG C~50 DEG C constant temperature, continues stirring reaction 2h~3.5h, obtains organic two Property copolymerized macromolecule first network gel, then cooled down, in the case where nitrogen is passed through, by the first network gel input be equipped with D The aqueous solution that component and deionized water are prepared can be swelling in closed reactor, the weight concentration of D components is 1.8%~11%, is pressed Weight meter, first network gel:Weight ratio=1 of D component deionized water solutions:（95~155）, swelling time is 2h~6h, then The aqueous solution prepared by component E and deionized water is added to continue swelling, the weight concentration of component E is 10%~20%, swelling time Be 16 h~24 h, it is swelling after the completion of, be warming up to 75 DEG C~95 DEG C, control ph is 3~7, in 75 DEG C~95 DEG C constant temperature, reaction 4h~6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel；The component A is by methylacryoyloxyethyl trimethyl chlorine Change ammonium, methacrylic acid oxygen ethyl trimellitic anhydride ester, crotonic acid composition, by the gauge of material, methylacryoyloxyethyl three Ammonio methacrylate:Methacrylic acid oxygen ethyl trimellitic anhydride:The ratio between amount of material of crotonic acid=（0.5~1.2）:（0.3~ 1.6）:（0.4~1.1）, B component is PEGDMA-400, and number-average molecular weight is 2000~20000, and it feeds intake Gross weight is the 2.5%~11% of component A gross weight, and component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is A The 0.3%~1.8% of component weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D Component is made up of abscisic acid, mannitol, methacrylic acid oxygen propyl group trimellitic anhydride ester and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, By the gauge of material, abscisic acid:Mannitol:The ratio between amount of material of methacrylic acid oxygen propyl group trimellitic anhydride ester=（0.5~ 2.0）:（0.08~0.32）:（0.4~1.1）, by weight, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester charged material weight be abscisic acid, Mannitol, three kinds the 1.8%~5.5% of total monomer weight of methacrylic acid oxygen propyl group trimellitic anhydride ester, component E is by persulfuric acid Potassium, pyridoxine hydrochloride composition, potassium peroxydisulfate charged material weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride is thrown Material weight is the 0.8%~5.6% of D component weights.