CN116874690A - Degradable antibacterial composite super absorbent resin and preparation method thereof - Google Patents
Degradable antibacterial composite super absorbent resin and preparation method thereof Download PDFInfo
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- CN116874690A CN116874690A CN202310760358.3A CN202310760358A CN116874690A CN 116874690 A CN116874690 A CN 116874690A CN 202310760358 A CN202310760358 A CN 202310760358A CN 116874690 A CN116874690 A CN 116874690A
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- 239000011347 resin Substances 0.000 title claims abstract description 130
- 229920005989 resin Polymers 0.000 title claims abstract description 130
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 95
- 239000002250 absorbent Substances 0.000 title claims abstract description 85
- 230000002745 absorbent Effects 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000010521 absorption reaction Methods 0.000 claims abstract description 40
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000000463 material Substances 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
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- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 5
- 229940117986 sulfobetaine Drugs 0.000 claims description 5
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- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
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- 229960003237 betaine Drugs 0.000 claims description 3
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- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 18
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- 241000255789 Bombyx mori Species 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 3
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- 206010021639 Incontinence Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
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- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 102000004142 Trypsin Human genes 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a degradable antibacterial composite super absorbent resin and a preparation method thereof. The preparation method comprises the steps of carrying out thermal initiation copolymerization and crosslinking on acrylic acid, acrylamide, hydrolyzed silk fibroin and unsaturated antibacterial monomers containing amphoteric ions or cations under the action of a crosslinking agent and an initiator to obtain hydrogel, then partially neutralizing carboxyl in the hydrogel by using sodium hydroxide solution, and then drying and crushing to obtain the degradable antibacterial composite super absorbent resin. The resin has the advantages that the absorption rate of deionized water can reach 550g/g, the absorption rate of NaCl solution (0.9%) can reach 100g/g, and the antibacterial rate to escherichia coli can reach 99.87%. The hydrolyzed silk fibroin and the unsaturated antibacterial monomer containing amphoteric ions or cations contained in the resin effectively improve the degradability and antibacterial activity of the super absorbent resin, and can be applied to the field of disposable sanitary products such as paper diapers/sheets, female sanitary napkins and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis of high-hydroscopicity resin, and particularly relates to a degradable antibacterial composite high-hydroscopicity resin and a preparation method thereof.
Background
The super absorbent resin is a functional polymer material with a three-dimensional network structure, has strong water absorption and water retention property because the structure of the super absorbent resin contains strong water absorption groups such as carboxyl, amino, hydroxyl and the like, and can absorb water molecules which are hundreds or even thousands of times of the mass of the super absorbent resin, so the super absorbent resin is widely applied to the fields of daily chemical products, agricultural water retention and the like. Superabsorbent resins can be classified according to source of raw materials into synthetic and natural superabsorbent resins. The polyacrylic acid type super absorbent resin has the advantage of high water absorption rate due to the super absorbent property, and becomes a representative synthetic super absorbent resin. However, the conventional acrylic super absorbent resin has a very stable cross-linked structure, and the raw materials are derived from non-renewable petroleum-based derivatives, so that the conventional acrylic super absorbent resin is applied to disposable water absorbent articles, and is difficult to degrade after being discarded in a large amount, thereby causing serious environmental pollution, which does not conform to the green sustainable development concept proposed by our country. The natural polymer (starch, cellulose, protein, sodium alginate) is biodegradable material, and can be compounded with the synthetic polymer to make the synthetic super absorbent resin have certain degradability. Silk fibroin is a natural high molecular fiber protein extracted from silk, the content of which is about 70% -80% of silk, and 18 amino acids are contained, wherein glycine (Gly), alanine (Ala) and serine (Ser) are about more than 80% of the total composition, and various amino acid residues on the amino acids are effective natural moisturizing factors, so that the silk fibroin has unique water absorption and water retention. In addition, the silk fibroin has biocompatibility and controllable biodegradability, and can induce the degradation of a synthetic high-molecular polymer compounded with the silk fibroin. Patent CN101531745A (preparation of silk fibroin/acrylic acid/acrylamide composite gel water-absorbing material) discloses a high-water-absorbing composite gel material for absorbing and retaining water, the composite water-absorbing gel material has higher water-absorbing capacity (500-800 g/g), however, the used silk fibroin solution is obtained by degumming, dissolving, filtering, dialyzing, concentrating and other steps of waste silkworm cocoon silk, the process flow is complex, the molecular weight of the obtained silk fibroin is difficult to control, and the water-absorbing gel material synthesized by the patent has no antibacterial property.
In the consumer market of superabsorbent resins, the production of baby diapers/pants represents 70.0% of the total consumption; for producing adult incontinence articles, 17.0% of the total consumption; the total consumption of the product is 7.0 percent. The infant diaper becomes the largest consumer market for superabsorbent resins. Meanwhile, as the world population ages, future adult incontinence articles are likely to pull on the continuous increase in the demand for superabsorbent resins. In these application scenarios, the superabsorbent resin inevitably contacts urine and blood of human body, and is susceptible to microbial infection and possible inflammatory reaction for infants and the elderly with low immunity. Therefore, the performance requirement of the super absorbent resin is that the super absorbent resin has not only good water absorption and water retention but also an antibacterial property. At present, the antibacterial property of the super absorbent resin is mainly imparted by surface modification and synthesis. The surface modification is mainly carried out by soaking, spraying or surface grafting. The patent CN113980340A, a water-absorbing sponge suitable for plant growth and a preparation method thereof, endows the granular sponge with antibacterial performance by soaking the granular sponge in zwitterionic monomer sulfobetaine methacrylic acid solution for surface grafting. However, the surface antibacterial modification of the sponge prepared by the soaking method has the problem that the grafting number of the monomer is unstable and the grafting degree is uncontrollable, so that the antibacterial effect is unstable. The synthesis method is to add an antibacterial agent in the synthesis process to participate in network construction. The antibacterial performance of the antibacterial super absorbent resin product prepared by the synthesis method is controllable and stable. The adopted antibacterial agents are mainly divided into inorganic, organic and natural antibacterial agents. The inorganic antibacterial agent mainly adopts metal ions such as silver, zinc and the like, and has high antibacterial rate and remarkable antibacterial effect. However, oxidative discoloration occurs during use and is costly. The natural antibacterial agent is environment-friendly, but has higher processing cost. The organic antibacterial agent has low cost and wide sources, and can be integrated into a resin network through a synthesis method, so that the organic antibacterial agent has a long-acting antibacterial effect. The patent CN109503686A 'an environment-friendly high-antibacterial super absorbent resin and a preparation method thereof' grafts the lignin sulfonate modified by the epoxy quaternary ammonium salt onto the polyacrylate super absorbent resin, thereby improving the biodegradability and antibacterial activity of the super absorbent resin. However, the process flow for preparing the super absorbent resin by the method is complex, and the steps of modification reaction, reduced pressure concentration, filtration washing, freeze drying and the like are needed, so that the investment time and equipment cost are high, and the popularization and the application in the market are not facilitated.
Disclosure of Invention
Aiming at the problems of poor degradability, high antibacterial cost and the like of the existing polyacrylic acid super absorbent resin, the invention prepares the composite super absorbent resin with both degradability and antibacterial property.
The invention aims to provide a preparation method of a degradable antibacterial composite super absorbent resin, which is characterized in that silk fibroin powder is compounded with acrylic acid and an acrylamide monomer, so that the water absorbability and degradability of the super absorbent resin are improved, the problem that the traditional acrylic super absorbent resin is not degradable is solved, and meanwhile, the technological process of introducing silk fibroin into the resin is simplified. The method does not need complex steps such as degumming and dissolving of silkworm cocoons, filtration and dialysis, drying and the like, but directly adds silk fibroin powder with the average particle size of 2-10 mu m into a composite monomer solution, and then carries out ultrasonic dispersion aggregation to obtain a uniform solution.
Besides degradability, the composite high water-absorbent resin further introduces the olefinically unsaturated antibacterial monomer containing amphoteric ions or cations through free radical polymerization reaction in the preparation process, so that the olefinically unsaturated antibacterial monomer participates in the three-dimensional network construction of the resin, on one hand, the high water-absorbent resin has long-term stable antibacterial performance, and on the other hand, anions and cations contained in the antibacterial monomer can be combined with a large number of water molecules through electrostatic interaction, so that the water absorption of the resin is improved. Therefore, the resin can be applied to the field of disposable absorbent articles such as paper diapers/sheets, sanitary napkins and the like.
The aim of the invention is realized by the following technical scheme:
a preparation method of degradable antibacterial composite super absorbent resin specifically comprises the following steps:
sequentially adding acrylic acid, acrylamide, a cross-linking agent and a photoinitiator into deionized water, and stirring for 5-20min under ice water bath to obtain a mixed solution 1; then adding hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 0.5-2.0h under ice water bath to obtain a mixed aqueous solution 2; adding an unsaturated antibacterial monomer material containing amphoteric ions or cations into the solution 2, and then performing thermal initiation curing to obtain hydrogel; after the reaction is finished, the carboxyl in the hydrogel is neutralized by sodium hydroxide solution, and finally the hydrogel is dried and crushed to obtain the degradable antibacterial composite super absorbent resin.
Further, the mass of the acrylamide monomer accounts for 0.1-50% of the total mass of the acrylic acid and the acrylamide monomer.
Further, the cross-linking agent is one or more of N, N' -methylene bisacrylamide, triethylene glycol dimethacrylate, polyethylene glycol diacrylate and divinylbenzene; the initiator is one or more of potassium persulfate or ammonium persulfate; the cross-linking agent in the solution 1 accounts for 0.25-2.0 per mill of the total mass of the acrylamide and the acrylic acid monomer, and the initiator accounts for 0.5-2.5 per mill of the total mass of the acrylamide/the acrylic acid monomer.
Further, the hydrolyzed silk fibroin refers to hydrolyzed silk fibroin powder with a molecular weight of 30kDa-70kDa and an average particle size of 2-10 μm. The mass of the hydrolyzed silk fibroin accounts for 0.15% -30% of the total mass of the acrylic acid and the acrylamide.
Further, the unsaturated antibacterial monomer containing the zwitterion or the cation is one or more of dimethylaminoethyl methacrylate, sulfobetaine methacrylate, carboxylic betaine methacrylate, 2-methacryloyloxyethyl phosphorylcholine, diallyl dimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride; the mass of the unsaturated antibacterial monomer containing the amphoteric ion or the cationic ion accounts for 1.5-10% of the total mass of the acrylamide and the acrylic acid.
Further, the neutralization degree of carboxyl groups in the hydrogel is 50% -90%.
Further, the thermal initiation curing time is 0.5-3.0h, and the temperature of the thermal initiation curing is 55-80 ℃.
Further, the drying temperature is 80-105 ℃ and the drying time is 12-48h.
The degradable antibacterial composite super absorbent resin is prepared by the method. The resin has the advantages that the absorption rate of deionized water can reach 550g/g, the absorption rate of NaCl solution (0.9%) can reach 100g/g, and the antibacterial rate to escherichia coli can reach 99.87%.
The invention uniformly disperses the hydrolyzed silk fibroin powder with fixed molecular weight in acrylic acid and acrylamide monomer solution in an ultrasonic oscillation mode, and integrates unsaturated antibacterial monomers containing amphoteric ions or cations into a three-dimensional network structure of resin in the preparation process. The method simplifies the process flow of introducing the hydrolyzed silk fibroin into the resin, and the molecular weight of the hydrolyzed silk fibroin is controllable. Unsaturated antibacterial monomers are introduced in the preparation process, so that the unsaturated antibacterial monomers and acrylic acid and acrylamide monomers are subjected to free radical polymerization simultaneously, the technical problems of unstable grafting number and uncontrollable grafting degree in a soaking method are solved, and the preparation process of the degradable antibacterial super absorbent resin is simpler, and the antibacterial performance is more stable, controllable and long-lasting.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) On the basis of the traditional polyacrylic acid super absorbent resin, the hydrolyzed silk fibroin powder is introduced, so that on one hand, the raw material source of the super absorbent resin is enlarged, the biocompatibility and degradability of the composite polyacrylic acid super absorbent resin are improved, and compared with the synthetic water absorbent resin, the composite polyacrylic acid super absorbent resin is more environment-friendly and healthy. On the other hand, the process flow of resin introduction in the steps of degumming, dissolving, filtering, dialyzing, concentrating and the like of the waste silkworm cocoon silk is simplified, and the silk fibroin powder with stable and controllable molecular weight is introduced into the acrylic acid and acrylamide composite monomer solution in an ultrasonic dispersion mode to form a uniform mixed solution.
(2) Unsaturated antibacterial monomers containing amphoteric ions or cations are added in the process of synthesizing the resin, unsaturated double bonds on the antibacterial monomers simultaneously carry out free radical polymerization reaction with acrylic acid and acrylamide monomers under the action of an initiator and a cross-linking agent, and the unsaturated double bonds are integrated into a resin structure so as to participate in the three-dimensional network construction of the resin, so that the resin has stable and long-term antibacterial performance, and meanwhile, the defects of unstable grafting number and uncontrollable grafting degree existing in a soaking method are overcome.
(3) The degradable antibacterial composite super absorbent resin prepared by the invention does not need special equipment, has the advantages of easily available raw materials, low cost and simple preparation process. The degradable antibacterial composite super absorbent resin prepared by the invention has wide application prospect in the field of disposable sanitary products such as paper diapers/sheets, female sanitary napkins and the like.
Drawings
FIG. 1 is a scanning electron micrograph of the surface morphology of the degradable antibacterial composite super absorbent resin prepared in example 3.
FIG. 2 is a mass change curve of the degradable antibacterial composite super absorbent resin prepared in example 3 after 40 days of continuous degradation.
FIG. 3 shows the antibacterial effect of the degradable antibacterial composite super absorbent resin prepared in example 3 on Escherichia coli.
FIG. 4 shows the long-term antibacterial effect of the degradable antibacterial composite super absorbent resin prepared in example 4 on Escherichia coli.
Detailed Description
The invention is further described below in connection with specific examples which are intended to illustrate the invention and not to limit the scope of the invention, but to include any combination of the embodiments. The implementation conditions employed in the examples may be further adjusted according to the specific experimental environment. The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention and to make a clear and concise definition of the scope of the invention.
Example 1
5.994g of acrylic acid, 0.006g of acrylamide, 0.003g of N, N' -methylenebisacrylamide and 0.006g of ammonium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 10min under ice water bath to obtain a mixed solution 1; then adding 0.01g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 0.5h in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.2g of sulfobetaine methacrylate was added, and thermal initiation was performed at 55℃for 0.5h to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 1.3687g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, the hydrogel is dried for 12 hours at 80 ℃ and then crushed, so that the degradable antibacterial composite super absorbent resin is obtained. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 550g/g and a NaCl absorption rate of 40g/g (0.9%).
Example 2
Adding 4.5g of acrylic acid, 1.5g of acrylamide, 0.0015g of triethylene glycol dimethacrylate and 0.003g of ammonium persulfate into 16.0g of deionized water in sequence, and stirring for 5min under an ice water bath to obtain a mixed solution 1; then adding 1.8g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 1.0h in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.3g of a carboxylic betaine methacrylate was added, and thermal initiation was performed at 65℃for 1.0h, to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 2.2174g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, the hydrogel is dried for 24 hours at 105 ℃ and then crushed, and the degradable antibacterial composite super absorbent resin is obtained. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 400g/g and a NaCl absorption rate of 73g/g (0.9%).
Example 3
3.6g of acrylic acid, 2.4g of acrylamide, 0.005g of N, N' -methylene bisacrylamide and 0.010g of potassium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 15min under an ice water bath to obtain a mixed solution 1; then adding 0.8g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 1.5 hours in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.4g of dimethylaminoethyl methacrylate was added, and thermal initiation was performed at 70℃for 1.0h to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 1.5987g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, the hydrogel is dried for 36 hours at 90 ℃ and then crushed, and the degradable antibacterial composite super absorbent resin is obtained. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the experimental result shows that the resin has a deionized water absorption rate of 440g/g and a NaCl absorption rate of 85g/g (0.9%).
According to the current standard of YY/T1806.1-2021 (evaluation method for in vitro degradation Performance of biomedical materials: degradable polyesters in part 1), the degradation of the degradable antibacterial polyacrylic acid composite superabsorbent resin is tested by adopting a mass loss method. The experimental results showed that the mass remaining rate of the water-absorbent resin was 67.16% after about 40 days of continuous degradation in trypsin solution (1000U/ml). According to the current standard of GB 4789.3-2016 (food safety national Standard food microbiology inspection coliform group count), the antibacterial property of the degradable antibacterial polyacrylic acid composite super absorbent resin is tested by adopting a plate counting method. Experimental results show that the bacteriostasis rate of the resin on escherichia coli is 98.53%.
FIG. 1 is a scanning electron microscope image of the surface morphology of the degradable antibacterial composite super absorbent resin in example 3, and the resin can be seen from the image to have a relatively orderly three-dimensional network structure, uniform pore size and average size of 20-40 μm.
FIG. 2 is a graph showing the mass change of the degradable antibacterial composite super absorbent resin in example 3 after 40 days of continuous degradation, and the mass residual rate of the composite resin is 67.16% after 40 days of degradation. The composite resin retains the degradability of the silk fibroin, and thus the synthetic polymer network attached thereto becomes loose and degraded as the silk fibroin is degraded.
FIG. 3 is a graph showing the bacteriostatic effect of the degradable antibacterial composite super absorbent resin in example 3. After the colibacillus liquid is cultured for 24 hours under proper dilution times, the colony number is 136, and after the experimental group (namely, the antibacterial resin is put in the bacterial liquid for incubation) is cultured for 24 hours, the colony number is reduced to 2, the antibacterial rate is up to 98.53%, and the experimental result shows that the prepared super absorbent resin has obvious antibacterial effect.
Example 4
3.9g of acrylic acid, 2.1g of acrylamide, 0.007g of divinylbenzene and 0.015g of potassium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 20min under an ice water bath to obtain a mixed solution 1; then adding 1.2g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 2.0h in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.5g of 2-methacryloyloxyethyl phosphorylcholine was added, and thermal initiation was performed at 75℃for 2.5 hours to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 1.7319g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, the hydrogel is dried for 36 hours at 95 ℃ and then crushed, and the degradable antibacterial composite super absorbent resin is obtained. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 425g/g and a NaCl absorption rate of 92g/g (0.9%).
FIG. 4 shows the results of an antibacterial test for a long period of time on the degradable antibacterial composite super absorbent resin prepared in example 4. The prepared water-absorbent resin is respectively soaked in phosphoric acid buffer (PBS) for 1 day, 4 days, 7 days, 10 days and 13 days, and then taken out and dried, and the antibacterial effect of the resin soaked for different times is respectively tested by adopting a plate counting method according to the current standard of GB 4789.3-2016 food safety national Standard food microbiology test coliform count. As can be seen from the figure: the antibacterial rates on days 1, 4, 7, 10 and 13 were 99.03%, 99%, 98.9%, 98.7% and 99.87%, respectively. The antibacterial rate of the resin slightly decreased after 10 days of soaking, and was 98.7%, probably because a small amount of antibacterial monomer was not grafted into the network structure during the synthesis, and thus was dissolved in the PBS solution. After this time the antimicrobial ratio remained essentially unchanged, and remained at 98.7% on day 13. The above results indicate that the water-absorbent resin still has an antibacterial rate of 98.7% after being continuously immersed in the PBS solution for 13 days, indicating that the water-absorbent resin has a stable and long-lasting antibacterial effect.
Example 5
3.0g of acrylic acid, 3.0g of acrylamide, 0.012g of N, N' -methylene bisacrylamide and 0.007g of ammonium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 20min under an ice water bath to obtain a mixed solution 1; then adding 0.5g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 2.0h in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.6g of acryloyloxyethyl trimethyl ammonium chloride was added, and thermal initiation was performed at 80℃for 3.0 hours to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 1.3322g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, drying the hydrogel at 100 ℃ for 48 hours and then crushing to obtain the degradable antibacterial composite super absorbent resin. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 465g/g and a NaCl absorption rate of 101g/g (0.9%).
Example 6
1.2g of acrylic acid, 4.8g of acrylamide, 0.399 g of N, N' -methylene bisacrylamide and 0.012g of ammonium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 20min under an ice water bath to obtain a mixed solution 1; then adding 1.0g of hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 1.0h in an ice water bath to obtain a mixed aqueous solution 2; to the solution 2, 0.5g of sulfobetaine methacrylate was added, and thermal initiation was performed at 80℃for 1.5 hours, to obtain a hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 0.5256g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, drying the hydrogel at 95 ℃ for 48 hours and then crushing to obtain the degradable antibacterial composite super absorbent resin. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 300g/g and a NaCl absorption rate of 110g/g (0.9%).
Comparative example 1
3.0g of acrylic acid, 3.0g of acrylamide, 0.012g of N, N' -methylenebisacrylamide and 0.007g of ammonium persulfate are sequentially added into 16.0g of deionized water, and the mixture is stirred for 20min under an ice water bath to obtain a mixed solution 1, and the mixed solution is thermally initiated at 80 ℃ for 3.0h to obtain the hydrogel. After the reaction, the hydrogel was immersed in 50ml of a solution containing 1.3322g of sodium hydroxide to neutralize the carboxyl groups in the hydrogel. Finally, the hydrogel was dried at 100℃for 48 hours and then crushed to obtain a water-absorbent resin. The resin was subjected to a water absorption test according to the current standard JIS K7223-1996 method for testing the water absorption capacity of a super absorbent resin, and the test result shows that the resin has a deionized water absorption rate of 350g/g and a NaCl absorption rate of 50g/g (0.9%).
TABLE 1 data for Performance test of Water-absorbent resins
Note that: the antibacterial efficiency results in Table 1 show the antibacterial efficiency of the water-absorbent resin against Escherichia coli.
As is clear from Table 1, hydrolyzed silk fibroin and an unsaturated antibacterial monomer containing amphoteric or cationic are effective in improving the degradability and antibacterial activity of the water-absorbent resin. The double bonds contained in the unsaturated monomer are integrated into the three-dimensional network structure of the resin through free radical reaction, on one hand, the resin is endowed with long-term stable antibacterial activity, and on the other hand, anions and cations contained in the antibacterial monomer are combined with a large number of water molecules through electrostatic interaction, so that the water absorption of the resin is improved.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, but other variations and modifications are possible without departing from the technical solution described in the claims.
Claims (10)
1. The preparation method of the degradable antibacterial composite super absorbent resin is characterized by comprising the following steps of:
sequentially adding acrylic acid, acrylamide, a cross-linking agent and an initiator into deionized water, and stirring for 5-20min under ice water bath to obtain a mixed solution 1; then adding hydrolyzed silk fibroin powder into the solution 1, and carrying out ultrasonic treatment for 0.5-2.0h under ice water bath to obtain a mixed aqueous solution 2; adding an unsaturated antibacterial monomer material containing amphoteric ions or cations into the solution 2, and then performing thermal initiation curing to obtain hydrogel; after the reaction is finished, the carboxyl in the hydrogel is neutralized by sodium hydroxide solution, and finally the hydrogel is dried and crushed to obtain the degradable antibacterial composite super absorbent resin.
2. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the mass of the acrylamide monomer is 0.1% -50% of the total mass of the acrylic acid and the acrylamide monomer.
3. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the cross-linking agent is one or more of N, N' -methylene bisacrylamide, triethylene glycol dimethacrylate, polyethylene glycol diacrylate and divinylbenzene; the initiator is one or more of potassium persulfate or ammonium persulfate; the cross-linking agent in the solution 1 accounts for 0.25-2.0 per mill of the total mass of the acrylic acid and the acrylamide, and the initiator accounts for 0.5-2.5 per mill of the total mass of the acrylic acid and the acrylamide.
4. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the hydrolyzed silk fibroin is silk fibroin powder with a molecular weight of 30kDa-70kDa and an average particle size of 2-10 μm; the mass of the hydrolyzed silk fibroin accounts for 0.15% -30% of the total mass of the acrylic acid and the acrylamide.
5. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the unsaturated antibacterial monomer containing amphoteric ions or cations is one or more of dimethylaminoethyl methacrylate, sulfobetaine methacrylate, carboxylic betaine methacrylate, 2-methacryloyloxyethyl phosphorylcholine, diallyl dimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride; the mass of the unsaturated antibacterial monomer containing the amphoteric ion or the cationic ion accounts for 1.5-10% of the total mass of the acrylic acid and the acrylamide.
6. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the neutralization degree of carboxyl groups in the hydrogel is 50% -90%.
7. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the time of thermal initiation curing is 0.5-3.0h, and the temperature of thermal initiation curing is 55-80 ℃.
8. The method for preparing the degradable antibacterial composite super absorbent resin according to claim 1, wherein the drying temperature is 80-105 ℃ and the drying time is 12-48h.
9. The degradable antibacterial composite super absorbent resin prepared by the preparation method of any one of claims 1 to 8.
10. The degradable antibacterial composite super absorbent resin according to claim 9, wherein the absorption rate of deionized water of the resin is 550g/g, and the antibacterial rate of the resin to escherichia coli is 99.87%.
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