CN103788299B - The preparation method of natural plant antibacterial type High hydrophilous resin - Google Patents
The preparation method of natural plant antibacterial type High hydrophilous resin Download PDFInfo
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- CN103788299B CN103788299B CN201410008443.5A CN201410008443A CN103788299B CN 103788299 B CN103788299 B CN 103788299B CN 201410008443 A CN201410008443 A CN 201410008443A CN 103788299 B CN103788299 B CN 103788299B
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Abstract
The present invention provides the preparation method of natural plant antibacterial type High hydrophilous resin, acrylic acid solution is added after fully being dissolved in water by potassium hydroxide, the starch of gelatinizing is added after neutralization, wherein the ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide: acrylic acid=5～20:50.5～62.2:100 by weight；Regulation degree of neutralization is 65～80% afterwards, makes reaction obtain neutralizer completely, and cooling neutralizer is standby；Antibacterial, neutralizer, initiator and cross-linking agent carry out serial reaction to obtain natural plant antibacterial type High hydrophilous resin afterwards；And antibacterial is any one in oxymatrine, matrine or Radix Sophorae Flavescentis total alkaloids.The natural plant antibacterial type High hydrophilous resin that the present invention is obtained not only possesses high-hydroscopicity energy, but also has good fungistatic effect and biodegradability.
Description
[technical field]
The invention belongs to high molecular polymer based composites field, be specifically related to natural plant antibacterial type
The preparation method of High hydrophilous resin.
[background technology]
High hydrophilous resin is that a class has certain degree of cross linking, water insoluble, and the function of water swellability is high
Molecular material, can absorb substantial amounts of water, is now widely used for health care, agricultural gardening, food add
The fields such as work, environmental conservation, beauty and make-up, civil construction, oil exploitation.Starch-series High hydrophilous resin
It is primarily referred to as with starch as skeleton, by the family macromolecule material formed with other monomer graft copolymerization,
This kind of High hydrophilous resin absorbs water except the height with synthesizing super absorbent resin, outside the advantage of strong water conservation, also simultaneously
There is biodegradable characteristic, the pollution to environment can be reduced in using abandonment, and because starch is former
Material wide material sources, of a great variety, abundance, cheap, so its research always focus.By
It is a kind of polysaccharide in starch, it is easy to provide C source and N source to microorganism, so starch-series super absorbent resin
Fat is easy to breed bacteria and going mouldy, to starch-series High hydrophilous resin use and store cause the biggest
Problem.
In order to solve the problems referred to above, the water-absorbing resin with bacteriostasis property is prepared in practitioner's research and development, but
Often there is certain defect, such as: 1, Publication No. CN101559234A, entitled " novel height
Water-absorbing resin/antibacterial composite material and its production and use " Chinese patent, it is disclosed new
Type High hydrophilous resin be by water absorbing resin particle is added to containing silver ion, zinc ion, titanium oxide and
In the dispersion liquid of its mixture, stirring stands, and drying becomes the composite containing antibacterial；But this is multiple
Condensation material due to the water solublity of silver ion, soluble in water when running into water in and be not attached to absorbent material table
Face, and zinc ion, titanium oxide composite material are needed the most just possess antibacterial functions.2、
The Chinese patent of Application No. CN201110121713.X discloses one there is bacteriostasis property water suction tree
The preparation method and technology step of fat, the chitosan absorbent resin product of preparation possesses the same of high-hydroscopicity energy
Time also possess good fungistatic effect, but natural antibacterial agent-Chitosan-phospholipid complex class is prepared as due to it
This is higher, thus limits industrialized production.
Additionally, the application that synthetic antibacterial agents is in each field is more and more extensive, it is possible to solve some antibiotic properties and ask
Topic, but it also creates a series of problem, brings severe contamination to the living environment of the mankind: inorganic
Antibacterial, some has the biggest toxic and side effects, as metal ion hydrargyrum, silver, copper, lead etc. can have cause to skin
Carcinous, limited by resource simultaneously, application has certain difficulty；Though organic antibacterial agent has more than 30 year
Applicating history, (such as toxic and side effects, some monomer even has carcinogenesis) in addition to safety, there is also resistance to
The problems such as hot difference, easy decomposition and service life are short.
Various defect based on above-mentioned synthetic antibacterial agents, natural plant antibacterial arises at the historic moment therewith, sky
So plant-source antibacterial agent is compared with synthetic antibacterial agents, has lot of advantages: (1) is nontoxic, to skin
Without anaphylaxis and carcinogenecity；There is preferable biodegradability and Environmental compatibility；(2) environmental protection: it
Take from natural plant, be not chemosynthesis, extraction process and application process typically do not have harm people
The material of body and environment generates, and low cost.But, the domestic research to botanical fungicide is mainly
From natural plants, extract antibacterial be applied to the preventing and treating of agricultural disease, directly by containing pesticidal active substance
Plant or extract its effective ingredient and be processed into pesticide；Or difference active components of plants carried out organic and close
Reason compatibility post-treatment becomes pesticide；From natural plants extract antibacterial in preparing natural antiseptic agent also have should
With；But the active substance extracted in natural plants is applied to the research report in terms of high-efficiency water-absorbing resin
Not yet find.
[summary of the invention]
The technical problem to be solved is to provide the system of natural plant antibacterial type High hydrophilous resin
Preparation Method.
The present invention is by the following two technical scheme above-mentioned technical problem of solution:
One of technical scheme:
A kind of preparation method of natural plant antibacterial type High hydrophilous resin, including following concrete operations:
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5～20:50.5～62.2:100；Regulation degree of neutralization is 65～80% afterwards, makes reaction complete
Obtaining neutralizer, cooling neutralizer is standby；
Add to the antibacterial that concentration is 100～160mg/ml, in the neutralizer after cooling, add after stirring
Initiator, cross-linking agent carry out graft copolymerization, wherein antibacterial, neutralizer, initiator and cross-linking agent
The ratio of addition, be antibacterial by weight: neutralizer: initiator: cross-linking agent=9.5～38.1:50.5～
62.2:0.1～0.7:0.005～0.050；And graft copolymerization is carried out under the conditions of 65～80 DEG C, reaction
It is thick to solution, then proceedes to react the 1～6h starch graft acrylic acid obtaining there is bacteriostasis property
High hydrophilous resin the most described natural plant antibacterial type High hydrophilous resin；
Wherein, any one during antibacterial is oxymatrine, matrine or Radix Sophorae Flavescentis total alkaloids.
Further, gained natural plant antibacterial type High hydrophilous resin is placed in 65 DEG C of baking ovens dry to
Constant mass, then pulverizes and obtains powdery product.
Further, described initiator uses potassium peroxydisulfate.
Further, described cross-linking agent uses N, N '-methylene-bisacrylamide.
The two of technical scheme:
A kind of preparation method of natural plant antibacterial type High hydrophilous resin, including following concrete operations:
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5～20:50.5～62.2:100；Regulation degree of neutralization is 65～80% afterwards, makes reaction complete
Obtaining neutralizer, cooling neutralizer is standby；
Take the neutralizer after cooling and add initiator, cross-linking agent carries out graft copolymerization, wherein neutralize
The ratio of the addition of liquid, initiator and cross-linking agent, is neutralizer: initiator: cross-linking agent by weight
=50.5～62.2:0.1～0.7:0.005～0.050；And graft copolymerization enters under the conditions of 65～80 DEG C
OK, reaction is thick to solution, continues reaction 1～6h afterwards and obtains starch graft acrylic acid super absorbent resin
Fat；Then antibacterial that concentration is 100～160mg/ml is taken to this starch graft acrylic acid High hydrophilous resin
Carry out surface modification, it is thus achieved that the starch graft acrylic acid High hydrophilous resin with bacteriostasis property is the most described natural
Plant source antibacterial type High hydrophilous resin, and the weight of antibacterial and this starch graft acrylic acid High hydrophilous resin
Ratio is 0.0125～2:0.5～5；
Wherein, any one during antibacterial is oxymatrine, matrine or Radix Sophorae Flavescentis total alkaloids.
Further, gained natural plant antibacterial type High hydrophilous resin is placed in 65 DEG C of baking ovens dry to
Constant mass, then pulverizes and obtains powdery product.
Further, described initiator uses potassium peroxydisulfate.
Further, described cross-linking agent uses N, N '-methylene-bisacrylamide.
The beneficial effects of the present invention is: plant bacteriostatic agent and starch, acrylic acid by neutralize, cause with
The water-absorbing resin of the antibacterial type that crosslinked action synthesis obtains not only possesses high-hydroscopicity energy, but also tool is good
Fungistatic effect and biodegradability, additionally there is lower-cost feature.
[detailed description of the invention]
The preparation method of natural plant antibacterial type High hydrophilous resin of the present invention has the concrete technology of following two
Scheme:
One of technical scheme:
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5～20:50.5～62.2:100；Regulation degree of neutralization is 65～80% afterwards, makes reaction complete
Obtaining neutralizer, cooling neutralizer is standby；After the antibacterial that concentration is 100～160mg/ml is added to cooling
Neutralizer in, add initiator, cross-linking agent after stirring and carry out graft copolymerization, wherein antibacterial,
The ratio of the addition of neutralizer, initiator and cross-linking agent, is antibacterial: neutralizer by weight: cause
Agent: cross-linking agent=9.5～38.1:50.5～62.2:0.1～0.7:0.005～0.050；And graft copolymerization
Carrying out under the conditions of 65～80 DEG C, reaction is thick to solution, then proceedes to react 1～6h and is had
There is the starch graft acrylic acid High hydrophilous resin the most described natural plant antibacterial type super absorbent resin of bacteriostasis property
Fat；Antibacterial is any one in oxymatrine, matrine or Radix Sophorae Flavescentis total alkaloids.
The two of technical scheme:
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5～20:50.5～62.2:100；Regulation degree of neutralization is 65～80% afterwards, makes reaction complete
Obtaining neutralizer, cooling neutralizer is standby；Take the neutralizer after cooling and add initiator, cross-linking agent is carried out
Graft copolymerization, the wherein ratio of the addition of neutralizer, initiator and cross-linking agent, in being by weight
And liquid: initiator: cross-linking agent=50.5～62.2:0.1～0.7:0.005～0.050；And graft copolymerization is anti-
Should carry out under the conditions of 65～80 DEG C, reaction is thick to solution, and continuing reaction 1～6h afterwards must form sediment
Powder graft acrylic acid High hydrophilous resin；Then antibacterial that concentration is 100～160mg/ml is taken to this starch
Graft acrylic acid High hydrophilous resin carries out surface modification, it is thus achieved that have the starch graft acrylic acid of bacteriostasis property
High hydrophilous resin the most described natural plant antibacterial type High hydrophilous resin, and antibacterial with this starch-grafted third
The weight ratio of olefin(e) acid High hydrophilous resin is 0.0125～2:0.5～5；Wherein, antibacterial be oxymatrine,
Or any one in Radix Sophorae Flavescentis total alkaloids.
And in above two technical scheme: the natural plant antibacterial type High hydrophilous resin preparing gained is placed in
65 DEG C of baking ovens are dried to constant mass, then pulverizes and obtain powdery product；Initiator all uses over cure
Acid potassium；Cross-linking agent all uses N, N '-methylene-bisacrylamide.
The following is to measure the present invention and prepare natural plant antibacterial type High hydrophilous resin antibacterial of gained
Two kinds of methods of performance.
Bacteriostasis property assay method one:
Preparation, containing colibacillary antibacterial bacterium solution, makes initial bacterium solution containing bacterial concentration about 107The cfu/ml order of magnitude,
By the natural plant antibacterial type High hydrophilous resin of one of 0.10g technical scheme gained, 98ml normal saline
Solution and 1ml LB culture medium are placed in the conical flask of 300ml, add 1ml cultured after autoclaving
Initial bacterium solution, puts shaking table (37 DEG C, 150rpm) concussion and cultivates 8h, pipette 0.2ml bacterium solution from conical flask
Do 10-4Dilution after spread plate, each dilution factor is coated with three culture dishs, cultivates 24h in 37 DEG C of incubators,
Observe bacterial growth situation, calculate resin bacteriostasis rate.Blank identical with aforesaid operations but without pressing down
The starch-resin of microbial inoculum.Bacteriostasis rate computing formula is as follows: η=[(N1-N2)/N1]×100%
In formula: N1Blank starch-resin rear clump count antibacterial to escherichia coli；
N2Containing plant antibacterial type starch-resin to escherichia coli clump count after antibacterial.
Bacteriostasis property assay method two:
Three experimental grouies are set, often organize two institutes all weighing 0.1g blank starch-resin, 0.1g technical scheme
Natural plant antibacterial type High hydrophilous resin and be respectively placed in tea bag, ultraviolet under aseptic operating platform
Sterilizing 20min, then exposes in atmosphere, and the first experimental group exposes 2h, and the second experimental group exposes 12h,
3rd experimental group exposes 26h.With 20ml aseptic water washing resin, collect thalline, take 200 μ l eluents
It is coated with flat board, after 3d, observes the colony growth situation on flat board.
The following is several embodiments of two technical schemes of the present invention, and each embodiment prepares the sky of gained
So the bacteriostasis property of plant source antibacterial type High hydrophilous resin measures and uses in above two method corresponding one
Kind.
Embodiment 1
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5:54.4:100；Regulation degree of neutralization is 70% afterwards, makes reaction obtain neutralizer, cooling completely
Neutralizer is standby；The Radix Sophorae Flavescentis total alkaloids that concentration is 160mg/ml is added in the neutralizer after cooling, after stirring
Add initiator, cross-linking agent and carry out graft copolymerization, wherein Radix Sophorae Flavescentis total alkaloids, neutralizer, initiator and
The ratio of the addition of cross-linking agent, is Radix Sophorae Flavescentis total alkaloids: neutralizer: initiator: cross-linking agent=15.3 by weight:
54.4:0.3:0.02；And graft copolymerization reacts under the conditions of 70 DEG C, react thick to product,
Continue reaction 4h described natural plant antibacterial type High hydrophilous resin.After measured, this natural plants
The water absorbent rate of source antibacterial type High hydrophilous resin is 500g/g, bacteriostasis rate 35%.
Embodiment 2
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=15:58.3:100；Regulation degree of neutralization is 75% afterwards, makes reaction obtain neutralizer completely, cold
But neutralizer is standby；The matrine that concentration is 100mg/ml is added in the neutralizer after cooling, after stirring
Add initiator, cross-linking agent carries out graft copolymerization, wherein matrine, neutralizer, initiator and friendship
The ratio of the addition of connection agent, is matrine: neutralizer: initiator: cross-linking agent=15.3:58.3 by weight:
0.1:0.02；And graft copolymerization reacts under the conditions of 80 DEG C, react thick to product, continue anti-
Answer 4h described natural plant antibacterial type High hydrophilous resin.After measured, this natural plant is antibacterial
The water absorbent rate of type High hydrophilous resin is 535g/g, bacteriostasis rate 41.2%.
Embodiment 3
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=20:58.3:100；Regulation degree of neutralization is 75% afterwards, makes reaction obtain neutralizer completely, cold
But neutralizer is standby；The Radix Sophorae Flavescentis total alkaloids that concentration is 160mg/ml is added in the neutralizer after cooling, stirring
Rear addition initiator, cross-linking agent carry out graft copolymerization, wherein Radix Sophorae Flavescentis total alkaloids, neutralizer, initiator
With the ratio of the addition of cross-linking agent, it is Radix Sophorae Flavescentis total alkaloids by weight: neutralizer: initiator: cross-linking agent=30.5:
58.3:0.3:0.05；And graft copolymerization reacts under the conditions of 65 DEG C, react thick to product,
Continue reaction 4h described natural plant antibacterial type High hydrophilous resin.After measured, this natural plants
The water absorbent rate of source antibacterial type High hydrophilous resin is 311g/g, and places after 24 hours still in natural environment
There is certain fungistatic effect.
Embodiment 4
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=20:62.2:100；Regulation degree of neutralization is 80% afterwards, makes reaction obtain neutralizer completely, cold
But neutralizer is standby；Take the neutralizer after cooling and add initiator, cross-linking agent carries out graft copolymerization,
The wherein ratio of the addition of neutralizer, initiator and cross-linking agent, is neutralizer: initiator by weight:
Cross-linking agent=62.2:0.1:0.035；And graft copolymerization is carried out under the conditions of 70 DEG C, reaction is to solution
In thick, continue reaction 4h afterwards and obtain starch graft acrylic acid High hydrophilous resin；Then taking concentration is
The Radix Sophorae Flavescentis total alkaloids of 160mg/ml carries out surface modification to this starch graft acrylic acid High hydrophilous resin, it is thus achieved that tool
There is the starch graft acrylic acid High hydrophilous resin the most described natural plant antibacterial type super absorbent resin of bacteriostasis property
Fat, and the weight ratio of Radix Sophorae Flavescentis total alkaloids and this starch graft acrylic acid High hydrophilous resin is 2.57:100.Through surveying
Fixed, the water absorbent rate of this natural plant antibacterial type High hydrophilous resin is 496g/g, bacteriostasis rate 71.45%.
Embodiment 5
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=15:62.2:100；Regulation degree of neutralization is 80% afterwards, makes reaction obtain neutralizer completely, cold
But neutralizer is standby；Take the neutralizer after cooling and add initiator, cross-linking agent carries out graft copolymerization,
The wherein ratio of the addition of neutralizer, initiator and cross-linking agent, is neutralizer: initiator by weight:
Cross-linking agent=62.2:0.3:0.005；And graft copolymerization is carried out under the conditions of 75 DEG C, reaction is to solution
In thick, continue reaction 4h afterwards and obtain starch graft acrylic acid High hydrophilous resin；Then taking concentration is
The Radix Sophorae Flavescentis total alkaloids of 160mg/ml carries out surface modification to this starch graft acrylic acid High hydrophilous resin, it is thus achieved that tool
There is the starch graft acrylic acid High hydrophilous resin the most described natural plant antibacterial type super absorbent resin of bacteriostasis property
Fat, and the weight ratio of Radix Sophorae Flavescentis total alkaloids and this starch graft acrylic acid High hydrophilous resin is 20.52:100.Warp
Measuring, the water absorbent rate of this natural plant antibacterial type High hydrophilous resin is 498g/g, bacteriostasis rate 100%.
Embodiment 6
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5:62.2:100；Regulation degree of neutralization is 75% afterwards, makes reaction obtain neutralizer, cooling completely
Neutralizer is standby；Take the neutralizer after cooling and add initiator, cross-linking agent carries out graft copolymerization,
The wherein ratio of the addition of neutralizer, initiator and cross-linking agent, is neutralizer: initiator by weight:
Cross-linking agent=62.2:0.7:0.005；And graft copolymerization is carried out under the conditions of 80 DEG C, reaction is to solution
In thick, continue reaction 4h afterwards and obtain starch graft acrylic acid High hydrophilous resin；Then taking concentration is
The Radix Sophorae Flavescentis total alkaloids of 160mg/ml carries out surface modification to this starch graft acrylic acid High hydrophilous resin, it is thus achieved that tool
There is the starch graft acrylic acid High hydrophilous resin the most described natural plant antibacterial type super absorbent resin of bacteriostasis property
Fat, and the weight ratio of Radix Sophorae Flavescentis total alkaloids and this starch graft acrylic acid High hydrophilous resin is 20.52:100.Warp
Measuring, the water absorbent rate of this natural plant antibacterial type High hydrophilous resin is 320g/g, and at natural environment
Middle placement still had preferable fungistatic effect after 24 hours.
To sum up, plant bacteriostatic agent obtains with crosslinked action synthesis by neutralizing, causing with starch, acrylic acid
The water-absorbing resin of antibacterial type not only possess high-hydroscopicity energy, but also have good fungistatic effect and raw
Thing degradation property, additionally has lower-cost feature.
Claims (4)
1. the preparation method of a natural plant antibacterial type High hydrophilous resin, it is characterised in that: include as
Lower concrete operations:
Add acrylic acid solution after fully being dissolved in water by potassium hydroxide, after neutralization, add the starch of gelatinizing,
The wherein ratio of starch, potassium hydroxide and acrylic acid addition, is starch: potassium hydroxide by weight:
Acrylic acid=5～20:50.5～62.2:100；Regulation degree of neutralization is 65～80% afterwards, makes reaction complete
Obtaining neutralizer, cooling neutralizer is standby；
Take the neutralizer after cooling and add initiator, cross-linking agent carries out graft copolymerization, wherein neutralize
The ratio of the addition of liquid, initiator and cross-linking agent, is neutralizer: initiator: cross-linking agent by weight
=50.5～62.2:0.1～0.7:0.005～0.050；And graft copolymerization enters under the conditions of 65～80 DEG C
OK, reaction is thick to solution, continues reaction 1～6h afterwards and obtains starch graft acrylic acid super absorbent resin
Fat；Then antibacterial that concentration is 100～160mg/ml is taken to this starch graft acrylic acid High hydrophilous resin
Carry out surface modification, it is thus achieved that the starch graft acrylic acid High hydrophilous resin with bacteriostasis property is the most described natural
Plant source antibacterial type High hydrophilous resin, and the weight of antibacterial and this starch graft acrylic acid High hydrophilous resin
Ratio is 0.0125～2:0.5～5；
Wherein, antibacterial is Radix Sophorae Flavescentis total alkaloids.
The preparation side of a kind of natural plant antibacterial type High hydrophilous resin the most according to claim 1
Method, it is characterised in that: gained natural plant antibacterial type High hydrophilous resin is placed in 65 DEG C of baking ovens drying
To constant mass, then pulverize and obtain powdery product.
The preparation side of a kind of natural plant antibacterial type High hydrophilous resin the most according to claim 1
Method, it is characterised in that: described initiator uses potassium peroxydisulfate.
The preparation side of a kind of natural plant antibacterial type High hydrophilous resin the most according to claim 1
Method, it is characterised in that: described cross-linking agent uses N, N '-methylene-bisacrylamide.
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| CN104497212A (en) * | 2014-12-16 | 2015-04-08 | 广西大学 | Preparation method of bacteriostatic water-absorbent resin |
| CN106084133B (en) * | 2016-06-15 | 2018-09-14 | 东北林业大学 | A kind of synthetic method of biocidal property high hydroscopic resin |
| CN107312816A (en) * | 2017-07-28 | 2017-11-03 | 天津大学 | A kind of assay method of the bacterial inhibitor fungistatic effect extracted from plant |
| CN109081887B (en) * | 2018-08-10 | 2021-06-29 | 安徽富瑞雪化工科技股份有限公司 | High water absorption resin |
| CN109575494A (en) * | 2018-11-11 | 2019-04-05 | 浙江金晟环保股份有限公司 | It is a kind of applied to frozen meat can fat absorption water-absorbent material and preparation method thereof |
| CN109535495A (en) * | 2018-11-13 | 2019-03-29 | 浙江金晟环保股份有限公司 | Biodegradable water-absorbent material of biocidal property for chilled food and preparation method thereof |
| CN114874390B (en) * | 2022-06-14 | 2023-05-26 | 湖南师范大学 | Preparation method of Ag/AgCl-polyacrylic acid-starch antibacterial super absorbent resin |
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| CN102229689B (en) * | 2011-05-11 | 2013-01-09 | 华侨大学 | Preparation method of absorbent resin with bacteriostasis function |
| CN103374093A (en) * | 2012-04-16 | 2013-10-30 | 连宗旭 | Betaine antibacterial super absorbent polymer (SAP) and preparation method thereof |
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