CN106750006A - 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, ethoxyethyl methacrylate, and chlorogenic acid as comonomers, and polyethylene glycol dimethacrylate as a crosslinking agent. Potassium sulfate-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; It swells in the aqueous solution prepared by pentaerythritol methacrylate and deionized water. The monomers and crosslinking agents in the aqueous solution undergo copolymerization and esterification under the action of potassium sulfate and pyridoxine hydrochloride, and finally obtain organic amphoteric copolymerization Polymer 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 methacryloyloxyethyl trimethyl ammonium chloride, methoxyethyl methacrylate, and chlorogenic acid. According to the amount of substances, methacryloyloxyethyl trimethyl Ammonium chloride: ethoxyethyl methacrylate: chlorogenic acid ratio = (0.5 ~ 1.2): (0.3 ~ 1.6): (0.4 ~ 1.1); B component is dimethacrylic acid poly Ethylene glycol ester, the number average molecular weight is 2000-20000, and its feeding weight is 2.5%-11% of the total weight of A component; C component is composed of potassium persulfate-sodium bisulfite, and its total feeding weight is A group 0.3% to 1.8% of the total weight, by weight, the weight ratio of potassium persulfate: sodium bisulfite = 1: (0.2 ~ 1.1); D component is composed of fumaric acid, quinic acid, vinylpyrrolidone Composed of pentaerythritol tetramethacrylate, based on the amount of substance, the ratio of fumaric acid: quinic acid: vinylpyrrolidone = (0.3～1.3): (0.08～0.32): (0.4～1.1) , by weight, the feed weight of pentaerythritol tetramethacrylate is 1.8% to 5.5% of the total weight of the three monomers of fumaric acid, quinic acid, and vinylpyrrolidone; E component is composed of potassium persulfate, pyridoxine salt Salt composition, the feed weight of potassium persulfate is 0.1%-1.2% of the total weight of component D, and the total weight of pyridoxine hydrochloride is 0.8%-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, ethoxyethyl methacrylate CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ OCH ₂ CH ₃ , chlorogenic acid (HO) ₂ C ₆ H ₃ CH=CHCOOCH(CH) ₂ (OH) ₂ ( CH ₂ ) ₂ C(OH)COOH comonomer and deionized water are prepared under stirring to form a uniformly mixed aqueous solution; after vacuuming and deoxygenation, nitrogen protection is introduced, and cross-linking agent polyethylene glycol dimethacrylate is added After heating up, add the redox initiator potassium persulfate-sodium bisulfite K ₂ S ₂ O ₈ -NaHSO ₃ aqueous solution, after initiation and copolymerization chain growth reaction, the cross-linking agent polyethylene dimethacrylate The glycol ester participates in the copolymerization reaction and the crosslinking reaction of the linear copolymerization macromolecules to form a crosslinking network structure, and through the chain termination reaction, the first network gel of the organic amphoteric copolymerization macromolecules is obtained. Nitrogen protection, organic amphoteric copolymer first network gel in fumaric acid HOOCCH=CHCOOH, quinic acid (HO) ₄ C ₆ H ₇ COOH, vinylpyrrolidone CH ₂ =CH-(C ₄ H ₆ NO ), pentaerythritol tetramethacrylate (CH ₂ =C(CH ₃ )COOCH ₂ ) ₄ C under the action of aqueous solution swelling, 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 continues to swell. The interior of the network gel is evenly distributed; after the temperature rises, linear copolymerization macromolecules are formed by initiation and copolymerization chain growth reaction, and the cross-linking agent pentaerythritol tetramethacrylate participates in the copolymerization reaction and cross-linking reaction of linear copolymerization macromolecules, forming Cross-linked network structure, pyridoxine hydrochloride catalyzes the esterification reaction between molecules with carboxyl groups and molecules with hydroxyl groups, due to the reaction between quinic acid with four OH groups and molecules with carboxyl groups Cross-linked network structure; further reaction, and 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 methods of the prior art, the outstanding advantages of the present invention are that the monomer methacryloyloxyethyltrimethylammonium chloride and the crosslinking agent pentaerythritol tetramethacrylate used in the preparation technology have low toxicity, and the monomer chlorogenic acid , fumaric acid, ethoxyethyl methacrylate, vinylpyrrolidone and cross-linking agent polyethylene glycol dimethacrylate, quinic acid are non-toxic, which reduces the toxicity of the gel; the prepared interpenetrating network gel The free radical cross-linking and esterification cross-linking network structure 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: 125g methacryloyloxyethyltrimethylammonium chloride, 63g ethoxyethyl methacrylate, 177g chlorogenic acid and 852ml 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%, vacuumize to a relative vacuum of -0.03MPa, then pass nitrogen gas to restore the reactor to normal pressure, add 11g of polyethylene dimethacrylate with a number average molecular weight of 4000 Alcohol ester and 41ml of deionized water prepared aqueous solution, the weight concentration of the aqueous solution is 21%, then warming up to 40 ° C, adding 1.4g potassium persulfate, 0.42g sodium bisulfite and 31ml deionized water prepared aqueous solution, the aqueous solution The weight concentration of the organic amphoteric copolymer 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 2.2 hours to obtain the first network gel of the organic amphoteric copolymer polymer; then cooled, and the organic amphoteric copolymer high Molecular first network gel 62g drops into the volume and is swollen in the sealable reactor of 15L, is housed in this reactor 46g fumaric acid, 19g quinic acid, 56g vinylpyrrolidone, 2.42g pentaerythritol tetramethacrylate and 6058ml An aqueous solution prepared with deionized water, the weight concentration of the aqueous solution is 2%, the weight of the first network gel (62g): the weight of the aqueous solution (6182g) = 1:100, swelling for 2.5h; then add 0.25g of potassium persulfate , 1.24g of pyridoxine hydrochloride and 13ml of deionized water to prepare the aqueous solution to continue swelling, the weight concentration of the aqueous solution is 10.5%, swelling for 17 h; After constant temperature reaction for 4.2 hours, an organic amphoteric copolymer interpenetrating network gel was obtained. The gel is insoluble in water and can swell in water. The gel swelling rate (ESR) = 7813% (deionized water), and the gel swelling rate (ESR) = 7694% (1% NaCl aqueous solution by weight).

Example 2: 228g methacryloyloxyethyltrimethylammonium chloride, 237g ethoxyethyl methacrylate, 354g chlorogenic acid and 547ml of deionized water are added to a 2L sealable reactor Stir and mix evenly in the medium, the weight concentration of the aqueous solution is 60%, vacuumize to a relative vacuum of -0.07MPa, then pass nitrogen into the reactor to restore the reactor to normal pressure, add 82g of polyethylene dimethacrylate with a number average molecular weight of 17000 Alcohol ester and 128ml of deionized water prepared aqueous solution, the weight concentration of the aqueous solution is 39%; then warm up to 48 ℃, add 6.15g potassium persulfate, 6.15g sodium bisulfite and 73ml deionized water prepared aqueous solution, the aqueous solution The weight concentration of the organic amphoteric copolymer is 14.5%; at a constant temperature of 48°C, the pH value is controlled at 8.5, 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 the organic amphoteric copolymer high Molecular first network gel 22g drop-in volume is in the airtight reactor of 5L and swells, and 139g fumaric acid, 58g quinic acid, 111.14g vinylpyrrolidone, 15.4g pentaerythritol tetramethacrylate and 2911ml An aqueous solution prepared with deionized water, the weight concentration of the aqueous solution is 10%, the weight of the first network gel (22g): the weight of the aqueous solution (3235g) = 1:150, swelling for 5.5h; then add 0.65g of potassium persulfate , 3.23g of pyridoxine hydrochloride and 16ml of deionized water to prepare the aqueous solution to continue swelling, the weight concentration of the aqueous solution is 19.5%, swelling for 23 h; After constant temperature reaction for 5.5 hours, organic amphoteric copolymerized polymer interpenetrating network gel was obtained. The gel is insoluble in water and can swell in water. The gel swelling rate (ESR) = 6780% (deionized water), and the gel swelling rate (ESR) = 6653% (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, ethoxyethyl methacrylates, chlorogenic acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride Ammonium:Ethoxyethyl methacrylates:The ratio between amount of material of chlorogenic 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 its gross weight that feeds intake is A groups Divide the 2.5%~11% of gross weight, component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is component A gross weight 0.3%~1.8%, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D components are by rich horse Acid, chinic acid, vinyl pyrrolidone and pentaerythritol tetramethacrylate composition, by the gauge of material, fumaric acid:Kui Ni Acid:The ratio between amount of material of vinyl pyrrolidone=（0.3~1.3）:（0.08~0.32）:（0.4~1.1）, by weight, Pentaerythritol tetramethacrylate charged material weight is fumaric acid, chinic acid, three kinds of total monomer weights of vinyl pyrrolidone 1.8%~5.5%, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate charged material weight is D component weights 0.1%~1.2%, pyridoxine hydrochloride charged material weight is the 0.8%~5.6% of D component weights.