CN106750029A - 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, 2-ethylhexyl methacrylate, itaconic acid as comonomers, and polyethylene glycol dimethacrylate as cross-linking agent Potassium persulfate-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; ‑β‑hydroxypropyl ester, neopentyl glycol dimethacrylate and deionized water are swollen in the aqueous solution, and the monomer and crosslinking agent in the aqueous solution undergo co-production through the action of potassium sulfate and pyridoxine hydrochloride. Polymerization, esterification reaction, and finally an organic amphoteric copolymerized polymer interpenetrating network gel is obtained.

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 put into the sealable reactor that the aqueous solution that D component and deionized water are prepared is housed swelling, the weight of D component The concentration is 1.8%~11%, by weight, the weight ratio of the first network gel: D component deionized aqueous solution = 1: (95~155), swelling for 2h~6h; then add E component and deionized water The aqueous solution prepared with water continues to swell, the weight concentration of component E is 10% to 20%, and the swelling time is 16 h to 24 h; ～95°C constant temperature, react for 4h～6h, and obtain organic amphoteric copolymerized polymer interpenetrating network gel. The A component is composed of methacryloyloxyethyltrimethylammonium chloride, methacrylic acid-2-ethylhexyl, and itaconic acid. Methyl ammonium chloride: 2-ethylhexyl methacrylate: the ratio of the amount of itaconic acid = (0.5 ~ 1.2): (0.3 ~ 1.6): (0.4 ~ 1.1); B component is two Polyethylene glycol methacrylate, the number average molecular weight is 2000-20000, and its feed weight is 2.5%-11% of the total weight of A component; C component is composed of potassium persulfate-sodium bisulfite, and its feed total The weight is 0.3% to 1.8% of the total weight of component A. By weight, the weight ratio of potassium persulfate: sodium bisulfite = 1: (0.2 to 1.1); component D consists of jasmonic acid, D-arabinose , methacrylate-β-hydroxypropyl ester and dimethacrylate neopentyl glycol ester, according to the amount of substance, jasmonic acid: D-arabinose: the amount of substance of methacrylate-β-hydroxypropyl ester Ratio=(0.3～1.3):(0.08～0.32):(0.4～1.1), by weight, the feeding weight of neopentyl glycol dimethacrylate is jasmonic acid, D-arabinose, methacrylic acid-β- 1.8% to 5.5% of the total weight of the three monomers of hydroxypropyl ester; component E is composed of potassium persulfate and pyridoxine hydrochloride, and the weight of potassium persulfate is 0.1% to 1.2% of the total weight of component D. The feed weight of pyridoxine hydrochloride is 0.8% to 5.6% of the total weight of component D.

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, 2-ethylhexyl methacrylate CH ₂ =C(CH ₃ )COOCH ₂ CH(C ₂ H ₃ )(CH ₂ ) ₃ CH ₃ , itaconic acid H ₂ C=C(COOH)CH ₂ Aqueous solution of COOH comonomer; after vacuuming and deoxygenation, pass nitrogen protection, add crosslinking agent polyethylene glycol dimethacrylate aqueous solution; after heating up, add redox initiator potassium persulfate-hydrogen sulfite The aqueous solution of sodium K ₂ S ₂ O ₈ -NaHSO ₃ undergoes initiation and copolymerization chain growth reaction, and the cross-linking agent polyethylene glycol dimethacrylate participates in the copolymerization reaction and the linear copolymerization macromolecule cross-linking reaction to form cross-linking The network structure, through the chain termination reaction, obtains the first network gel of the organic amphoteric copolymer polymer. Nitrogen protection, organic amphoteric copolymer first network gel in jasmonic acid HOOCCH ₂ -(C ₅ H ₆ O)CH ₂ CH=CHC ₂ H ₅ , D-arabinose (HO) ₄ C ₅ H ₆ O , β-hydroxypropyl methacrylate CH ₂ =C(CH ₃ )COOCH ₂ CH(OH)CH ₃ , neopentyl glycol dimethacrylate CH ₂ =C(CH ₃ )COOCH ₂ C(CH ₃ ) ₂ CH ₂ OOC(CH ₃ )C=CH ₂ solution to swell, then add initiator potassium persulfate K ₂ S ₂ O ₈ , catalyst pyridoxine hydrochloride (CH ₃ )(HOCH ₂ ) ₂ ( Continue to swell under the action of HO)C ₅ HN·HCl aqueous solution. During the swelling process, monomers, cross-linking agents, initiators, and catalysts in the aqueous solution enter into the interior of the organic amphoteric copolymer polymer first network gel and distribute uniformly; Initiation, copolymerization chain growth reaction to form a linear copolymerization macromolecule, the cross-linking agent neopentyl glycol dimethacrylate participates in the copolymerization reaction and the cross-linking reaction of the linear copolymerization macromolecule, forming a cross-linked network structure, pyridoxine salt Salt catalyzes the esterification reaction between molecules with carboxyl groups and molecules with hydroxyl groups. Since D-arabinose has four OH groups, it will form a cross-linked network structure with molecules with carboxyl groups; further reactions, Finally, due to the chain termination of the free radical copolymerized macromolecule and the completion of the esterification reaction, an organic amphoteric copolymerized polymer interpenetrating network gel is formed.

Compared with the prior art method, the outstanding advantage of the present invention is that the monomer methacryloxyethyltrimethylammonium chloride, methacrylic acid-2-ethylhexyl, jasmonic acid, methacrylic acid used in the preparation technology - β-hydroxypropyl ester and cross-linking agent neopentyl glycol dimethacrylate, monomer itaconic acid and cross-linking agent polyethylene glycol dimethacrylate are non-toxic, and D-arabinose is non-toxic, reducing Gel toxicity; the prepared interpenetrating network gel has a free radical crosslinking and esterification crosslinking 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. Environmental and economic benefits.

detailed description

Example 1: 124.5g of methacryloyloxyethyltrimethylammonium chloride, 79.3g of 2-ethylhexyl methacrylate, 65g of itaconic acid and 627.3ml of deionized water were added to a 1.5L Stir and mix evenly in a closed reactor, the weight concentration of the aqueous solution is 30%; vacuumize to a relative vacuum degree of -0.03MPa, then feed nitrogen into the reactor to restore the reactor to normal pressure, add 8.1g of di An aqueous solution prepared from polyethylene glycol methacrylate and 30.3ml of deionized water, the weight concentration of the aqueous solution is 21%; then the temperature is raised to 37°C, and 1.03g of potassium persulfate, 0.31g of sodium bisulfite and 23.1ml of deionized water are added An aqueous solution prepared with ionized water, 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; Under nitrogen gas, 87.32g of organic amphoteric copolymer polymer first network gel was put into a 15L sealable reactor for swelling, and 84.11g of jasmonic acid, 15g of D-arabinose, 72.1g of methacrylic acid- The aqueous solution prepared by β-hydroxypropyl ester, 3.42g neopentyl glycol dimethacrylate and 8557ml deionized water, the weight concentration of this aqueous solution is 2%, the weight (87.32g) of the first network gel: the weight of this aqueous solution Weight (8732g) = 1:100, swelling for 3 hours; adding 0.35g of potassium persulfate, 1.75g of pyridoxine hydrochloride and 17.9ml of deionized water to continue swelling. The weight concentration of the aqueous solution is 10.5%. 17h; after the swelling was completed, the temperature was raised to 78°C, the pH value was controlled to 3.4, and the reaction was carried out at a constant temperature of 78°C for 4.3h 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) = 7357% (deionized water), and the gel swelling rate (ESR) = 7289% (1% NaCl aqueous solution by weight).

Example 2: 228.3g of methacryloyloxyethyltrimethylammonium chloride, 297.5g of 2-ethylhexyl methacrylate, 130.1g of itaconic acid and 437.2ml of deionized water were added to a volume of 1.5L Stir and mix evenly in a closed reactor, the weight concentration of the aqueous solution is 60%; vacuumize to a relative vacuum of -0.07MPa, then feed nitrogen to restore the reactor to normal pressure, add 65.6g of di An aqueous solution prepared from polyethylene glycol methacrylate and 102.6ml of deionized water, the weight concentration of the aqueous solution is 39%; then the temperature is raised to 47°C, and 4.92g of potassium persulfate, 4.92g of sodium bisulfite and 58ml of deionized water are added An aqueous solution prepared with water, the weight concentration of the aqueous solution is 14.5%, at a constant temperature of 47 ° C, the pH value is controlled to 9.4, and the stirring reaction is continued for 3.2 hours to obtain the first network gel of the organic amphoteric copolymer polymer; Under nitrogen, 30.9g of organic amphoteric copolymer polymer first network gel was put into a 10L sealable reactor to swell, and 252.3g of jasmonic acid, 45g of D-arabinose, and 144.2g of methacrylic acid-β-hydroxypropyl ester were housed in the reactor , 22.1g neopentyl glycol dimethacrylate and the aqueous solution prepared by 4172ml deionized water, the weight concentration of this aqueous solution is 10%, the weight of the first network gel (30.9g): the weight of this aqueous solution (4636.1g) =1: 150, swelling for 5.5h; add 0.93 potassium persulfate, 4.64g pyridoxine hydrochloride and 23ml deionized water to prepare the aqueous solution to continue swelling, the weight concentration of the aqueous solution is 19.5%, swelling for 23h; after swelling is completed Raise the temperature to 92°C, control the pH value to 6.5, and react at a constant temperature of 92°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) = 6395% (deionized water), and the gel swelling rate (ESR) = 6287% (1% NaCl aqueous solution by weight).

Claims (1)

1. A preparation method of an organic amphoteric copolymerized polymer interpenetrating network gel, which is characterized in that adding A component and deionized water in a sealable reactor and stirring to prepare an aqueous solution, controlling the weight concentration of A component to be 28%～ 62%, after the preparation of the solution is completed, vacuumize to a relative vacuum of -0.02MPa ~ -0.08MPa, inject nitrogen into the reactor to return to normal pressure, add the aqueous solution prepared by component B and deionized water under stirring, The weight concentration of component B is 20% to 40%. After the aqueous solution of component B is added, the temperature is raised to 35°C to 50°C, and the aqueous solution prepared by component C and deionized water is added under stirring. The weight concentration 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 the first network gel of the organic amphoteric copolymer polymer, and then cooled. Under nitrogen gas, put the first network gel into an airtight reactor containing an aqueous solution prepared by component D and deionized water to swell. The weight concentration of component D is 1.8% to 11%, by weight , the first network gel: the weight ratio of component D deionized aqueous solution = 1: (95 ~ 155), the swelling time is 2h ~ 6h, then add the aqueous solution prepared by E component and deionized water to continue swelling, E group The weight concentration is 10% to 20%, and the swelling time is 16 h to 24 h. After the swelling is completed, the temperature is raised to 75°C to 95°C, the pH value is controlled to be 3 to 7, and the temperature is kept at 75°C to 95°C for 4 hours. ~6h, organic amphoteric copolymer polymer interpenetrating network gel is obtained; the A component is composed of methacryloyloxyethyltrimethylammonium chloride, methacrylic acid-2-ethylhexyl ester, and itaconic acid , according to the amount of substance, methacryloyloxyethyltrimethylammonium chloride: 2-ethylhexyl methacrylate: the ratio of the amount of substance of itaconic acid=(0.5～1.2):(0.3 ～1.6): (0.4～1.1), B component is polyethylene glycol dimethacrylate, the number average molecular weight is 2000～20000, its feeding weight is 2.5%～11% of the total weight of A component, C group The component is composed of potassium persulfate-sodium bisulfite, and the total weight of the feed is 0.3% to 1.8% of the total weight of component A. By weight, the weight ratio of potassium persulfate:sodium bisulfite=1:(0.2 ～1.1), D component is composed of jasmonic acid, D-arabinose, β-hydroxypropyl methacrylate and neopentyl glycol dimethacrylate, based on the amount of substances, jasmonic acid: D-arabinose : Ratio of substance amount of methacrylate-β-hydroxypropyl ester=(0.3～1.3):(0.08～0.32):(0.4～1.1), by weight, neopentyl glycol dimethacrylate feeding weight It is 1.8% to 5.5% of the total weight of the three monomers of jasmonic acid, D-arabinose, and methacrylate-β-hydroxypropyl ester. The E component is composed of potassium persulfate, pyridoxine hydrochloride, potassium persulfate The feeding weight is 0.1%～1.2% of the total weight of D component, and the feeding weight of pyridoxine hydrochloride is 0.8%～5. 6%.