CN101613512A - A kind of rapid-imbibing foamed material with antibacterial property and preparation method thereof - Google Patents

A kind of rapid-imbibing foamed material with antibacterial property and preparation method thereof Download PDF

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CN101613512A
CN101613512A CN200910067281A CN200910067281A CN101613512A CN 101613512 A CN101613512 A CN 101613512A CN 200910067281 A CN200910067281 A CN 200910067281A CN 200910067281 A CN200910067281 A CN 200910067281A CN 101613512 A CN101613512 A CN 101613512A
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polyvinyl alcohol
preparation
imbibing
rapid
water
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CN101613512B (en
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王伟财
潘艳雄
彭超
姬相玲
罗云霞
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a kind of rapid-imbibing foamed material with antibacterial property and preparation method thereof.This material is to be raw material with polyvinyl alcohol and chitosan, is linking agent with formaldehyde, is the perforated foams with germ resistance of auxiliary material preparation with sulfuric acid, tensio-active agent, water; This material good permeability, water-intake rate are more than 1000%, and the time of suction height 50mm is less than 150 seconds, become softness, tough, resilient sponge after the imbibition.Material also has the characteristics of good inhibition bacterium, under experiment condition, bacterium reduces percentage more than 40%, heat-resisting, the UV resistant of material, can carry out disinfection with multiple mode, this material both can be used as surgical dressing, can be used as surgical hemostasis material, packing material etc. again, because it has no fibre shedding, the fast advantage of rate of liquid aspiration, the application in ophthalmology, Otorhinolaryngologic Department and other microsurgery more has its distinctive feature.

Description

A kind of rapid-imbibing foamed material with antibacterial property and preparation method thereof
Technical field
The invention belongs to the medical macromolecular materials field, relate to a kind of rapid-imbibing foamed material with antibacterial property and preparation method thereof.
Background technology
The hydrophilic foam structure has porousness, and liquid is had bigger absorptive capacity, almost can see through fully oxygen and carbonic acid gas, and its processing to Wound exudate is to control by the transhipment of water vapour and absorption.Foam materials is plastic or be processed into all thickness, the product of different shape, and wound had the excellent protection function, add antimicrobial component after, can reduce infectation of bacteria, promote the healing of wound.
Contain a large amount of oh groups on the polyvinyl alcohol molecular chain, therefore has good hydrophilicity, the foam materials of polyvinyl alcohol and formaldehyde condensation preparation had abundant pore texture and good chemical resistance, dry state is a kind of perforated foams of hard, can be used as filtering material, sound absorbent material, become a kind of softness after the suction and whippy spongy material, owing to have water-absorbent and high level expansion fast and in a large number, with the no adhesion of tissue, pliable and tough and solid, advantages such as no fibre shedding are fit to be applied to medical field very much.Simultaneously, can be applicable to cleaning material, suction handkerchief etc.
U.S. patent of invention US2609347, US4098728 and Chinese invention patent CN1095837A, CN1095075A disclose the preparation method of polyvinylalcohol formal foam, but in preparation process, do not add antimicrobial component, its anti-microbial property is unknowable.
Chinese invention patent CN1330105A discloses the preparation and the application of antibacterial polyvinyl alcohol material, adds the halogen amine compound in the Polyvinyl acetal process, has prepared the resin of the energy that has microbe killing properties, and it has the obvious sterilization performance by test shows.After long-time the use, through white water treatment, the antibacterial effect of can regenerating.But perforated foams is not made in this invention, does not therefore have a large amount of and the rapid absorption liquid ability, and in addition, its selected antiseptic-germicide also is not suitable for using at medical field.
Chinese invention patent CN101342381A discloses a kind of preparation method of anti-inflammation adhesion-proof hemostatic sponge, by the crosslinked of polyvinyl alcohol the chitosan gel rubber microballoon is fixed on the sponge inwall, and then immersion anti-inflammatory solution and anti solution, make PVA/ medicine carrying chitosan anti-inflammation adhesion-proof hemostatic sponge, this method is preparation chitosan gel rubber microballoon earlier, and to its surface grafting polyvinyl alcohol, then the chitosan gel rubber microballoon after the modification is fixed on the inwall of PVA sponge, obviously its preparation process is too complicated, and the anti-microbial property and the absorbent of material is not estimated.
Summary of the invention
One of purpose of the present invention provides a kind of rapid-imbibing foamed material with antibacterial property, and this material is the polymer composite foam material that comprises polyvinyl alcohol and chitosan.Contain abundant hydroxyl in the material, so material has excellent wetting ability; Material is made through physical blowing, has the open-celled structure of abundant mutual perforation, so material has higher imbibition capacity and imbibition ability fast; Owing to added the good chitosan of biocompatibility in the foams as antiseptic-germicide, given the anti-microbial property of material excellence.
The invention provides a kind of rapid-imbibing foamed material with antibacterial property, is to be raw material with polyvinyl alcohol and chitosan, is linking agent with formaldehyde, is the perforated foams of auxiliary material preparation with sulfuric acid, tensio-active agent, water; The massfraction of its component prescription is: polyvinyl alcohol 4-8%, chitosan 0.2-0.5%, formaldehyde 1-4%, tensio-active agent 1-2%, the water of sulfuric acid 15-25% and surplus.
The polyvinyl alcohol alcoholysis degree is 88-99%, and the polymerization degree is 1500-2000; Chitosan molecule amount 10,000-100,000, deacetylation is greater than 90%; Acid is sulfuric acid; Tensio-active agent is one or more in anionic, sodium dibutyl naphthalene sulfonate and non-ionic surfactant polyoxyethylene Span-20, the polyoxyethylene sorbitan monooleate.
Another object of the present invention provides a kind of preparation method of rapid-imbibing foamed material with antibacterial property, and its step and condition are as follows:
A) polyvinyl alcohol is dissolved in to be made into massfraction in 90 ℃-100 ℃ the distilled water be 7-15% solution;
B) by proportioning, adding massfraction in polyvinyl alcohol solution is 50% sulphuric acid soln, chitosan, tensio-active agent, stirs into emulsion form;
C) by proportioning, adding massfraction in emulsion is 37% formaldehyde, and continues to stir 10-30 minute;
D) emulsion of step c) is poured in the acidproof mould, at 30-60 ℃ of solidifying and setting 4-40 hour, through washing, drying obtained a kind of rapid-imbibing foamed material with antibacterial property.This material room temperature preservation.
Rapid-imbibing foamed material with antibacterial property of the present invention can be applied to surgical operation liner, Otorhinolaryngologic Department and other microsurgery fields such as hemostatic material, Medical dressing of sucking blood.
The performance test methods of rapid-imbibing foamed material with antibacterial property of the present invention is as follows:
Water-intake rate: the initial weight (A) of measuring the foam materials with a certain size afterwards, foam sample was soaked in distilled water 10 minutes, be placed on the water on filtering net last 30 second of scumming surface, and weigh (B), the water-intake rate of foam materials calculates with following formula: water-intake rate (%)=(B-A)/A * 100%.This process repeats 3 times, and the mean value calculation of 3 observed values is as water-intake rate.
Vertical rate of water absorption: vertical water absorbing properties is that a kind of showing can be with the standard of measurement of the ability of the direction fluid transfer opposite with gravity.Foam sample with 2cm * 20cm * 0.3cm size vertically immerses in the distilled water, picks up counting, and the working sample liquid draw is to the time that the time is spent apart from liquid level 50mm height.This process repeats 3 times, and the mean value calculation of 3 observed values is as vertical rate of water absorption.
Bacterium reduces percentage: adopt " antibacterial fabric method for testing performance " (FZ/T 01021-92) that foam materials of the present invention is carried out the germ resistance evaluation, bacterial classification is intestinal bacteria.
Beneficial effect
The germ resistance quick imbibition material of the present invention's preparation has good imbibition ability, water-intake rate is more than 1000%, rate of water absorption is fast, utilize testing method of the present invention, the time of the 50mm that vertically absorbs water is less than 150 seconds, can be used as the wound clean material, absorb wound sepage, purulence blood fast and in large quantities, also can be used as dressing, keep the wound circumference moist environment, promote the healing of wound.
The germ resistance quick imbibition material of the present invention's preparation has good antimicrobial property, and under the experiment condition, the bacterium decrement is more than 40%, and when patient carried out antibiotic therapy, the medical dressing with anti-microbial property can play auxiliary antibacterial effect.
What the germ resistance quick imbibition material of the present invention's preparation adopted all is the good materials of biocompatibility, to skin nonirritant and sensitization, has good medical use and is worth.
The technological process that the present invention prepares rapid-imbibing foamed material with antibacterial property is simple, and starting material are easy to get, and is not high to equipment requirements, is suitable for large-scale production.
Embodiment
Embodiment 1
The polyvinyl alcohol of 70 the gram polymerization degree 2000, alcoholysis degrees 99% are dissolved in and are made into 7% solution in 95 ℃ of hot water of 930 grams; Adding massfraction is 400 milliliters in 50% sulfuric acid, adds 5 gram chitosans, adds 10 gram sodium lauryl sulphate, 5 gram sodium dibutyl naphthalene sulfonates, mixes and pours in the agitator, stirs 20 minutes, and system becomes emulsion form; Adding massfraction is 60 milliliters of 37% formaldehyde solutions, continues to stir 10 minutes again; Pour aforesaid liquid into mould, put into thermostat container, 40 hours curing moldings of 30 ℃ of reactions, washing, drying obtains target product.
The performance test results sees Table 1.
Embodiment 2
The polyvinyl alcohol of 100 the gram polymerization degree 1700, alcoholysis degrees 99% are dissolved in and are made into 10% solution in 95 ℃ of hot water of 900 grams; Adding massfraction is 500 milliliters in 50% sulfuric acid, adds 5 gram chitosans, adds 10 gram sodium lauryl sulphate, 10 gram Tween-20s, mixes and pours in the agitator, stirs 20 minutes, and system becomes emulsion form; Adding massfraction is 100 milliliters of 37% formaldehyde solutions, continues to stir 10 minutes again; Pour aforesaid liquid into mould, put into thermostat container, 15 hours curing moldings of 40 ℃ of reactions, washing, drying obtains target product.
Embodiment 3
The polyvinyl alcohol of the polyvinyl alcohol of 300 the gram polymerization degree 1700, alcoholysis degrees 99% and the 200 gram polymerization degree 1700, alcoholysis degree 88% are dissolved in and are made into 10% solution in 95 ℃ of hot water of 4500 grams; Adding massfraction is 2500 milliliters in 50% sulfuric acid, add 20 gram chitosans, add 75 gram polyoxyethylene sorbitan monooleates, 25 gram Tween-20s, mix and pour in the agitator, stirred 20 minutes, system becomes emulsion form; Adding massfraction is 500 milliliters of 37% formaldehyde solutions, continues to stir 30 minutes again; Pour aforesaid liquid into mould, put into thermostat container, 10 hours curing moldings of 50 ℃ of reactions, washing, drying obtains target product.
The performance test results sees Table 1.
Embodiment 4
The polyvinyl alcohol of 300 the gram polymerization degree 1500, alcoholysis degrees 99% are dissolved in and are made into 12% solution in 95 ℃ of hot water of 2200 grams; Adding massfraction is 1800 milliliters in 50% sulfuric acid, adds 20 gram chitosans, adds 50 gram Tween-20s, mixes and pours in the agitator, stirs 20 minutes, and system becomes emulsion form; Adding massfraction is 200 milliliters of 37% formaldehyde solutions, continues to stir 20 minutes again; Pour aforesaid liquid into mould, put into thermostat container, 4 hours curing moldings of 60 ℃ of reactions, washing, drying obtains target product.
The performance test results sees Table 1.
Table 1 The performance test results:
Figure G2009100672811D00061

Claims (2)

1, a kind of rapid-imbibing foamed material with antibacterial property is to be raw material with polyvinyl alcohol and chitosan, is linking agent with formaldehyde, is the perforated foams of auxiliary material preparation with sulfuric acid, tensio-active agent, water; The massfraction of its component prescription is: polyvinyl alcohol 4-8%, chitosan 0.2-0.5%, formaldehyde 1-4%, tensio-active agent 1-2%, the water of sulfuric acid 15-25% and surplus;
The polyvinyl alcohol alcoholysis degree is 88-99%, and the polymerization degree is 1500-2000; Chitosan molecule amount 10,000-100,000, deacetylation is greater than 90%; Acid is sulfuric acid; Tensio-active agent is one or more in anionic, sodium dibutyl naphthalene sulfonate and non-ionic surfactant polyoxyethylene Span-20 and the polyoxyethylene sorbitan monooleate.
2, a kind of preparation method of rapid-imbibing foamed material with antibacterial property according to claim 1, its step and condition are as follows:
A) polyvinyl alcohol is dissolved in to be made into massfraction in 90 ℃-100 ℃ the distilled water be 7-15% solution;
B) by proportioning, adding massfraction in polyvinyl alcohol solution is 50% sulphuric acid soln, chitosan, tensio-active agent, stirs into emulsion form;
C) by proportioning, adding massfraction in emulsion is 37% formaldehyde, and continues to stir 10-30 minute;
D) emulsion of step c) is poured in the acidproof mould, at 30-60 ℃ of solidifying and setting 4-40 hour, through washing, drying obtained a kind of rapid-imbibing foamed material with antibacterial property.
CN2009100672811A 2009-07-16 2009-07-16 Rapid-imbibing foamed material with antibacterial property and preparation method thereof Active CN101613512B (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101912634A (en) * 2010-08-06 2010-12-15 华南理工大学 Method for preparing nanosilver/nano silicon dioxide-containing antibacterial biological dressing
CN101954115A (en) * 2010-10-22 2011-01-26 佘振定 Medical antibacterial sponge dressing and preparation method thereof
CN101967254A (en) * 2010-10-22 2011-02-09 佘振定 Medicinal microporous sponge and preparation method thereof
CN102871953A (en) * 2012-10-09 2013-01-16 姜志银 Super-absorbent adsorption suppository
CN104497348A (en) * 2014-12-31 2015-04-08 武汉奥绿新生物科技有限公司 Softening technology and equipment for polysaccharides lyophilized sponge dressing
CN104558988A (en) * 2013-10-11 2015-04-29 上海工程技术大学 High-elasticity strong-hydroscopicity chitosan sponge allowing normal-temperature drying and preparation method thereof
CN105194713A (en) * 2015-09-08 2015-12-30 广州润虹医药科技有限公司 Medical sponge with anti-microbial, heal-promoting and anti-adhesion functions and preparation method thereof
CN105999365A (en) * 2016-07-26 2016-10-12 四川艾医生医疗科技有限公司 Functional nasal cavity hemostatic material and preparation method thereof
CN107216479A (en) * 2017-07-26 2017-09-29 河北科技大学 A kind of preparation method of polyvinyl formal water suction foams
CN107224603A (en) * 2017-05-31 2017-10-03 武汉医佳宝生物材料有限公司 A kind of Medical negative pressure drainage composite foam material and preparation method thereof
CN107722342A (en) * 2017-10-13 2018-02-23 中国科学院长春应用化学研究所 A kind of porous anti-biotic material and preparation method thereof
WO2018113147A1 (en) * 2016-12-20 2018-06-28 欣乐加生物科技有限公司 Dry gel sponge of super water-absorbent polymer hydrogel, preparation method therefor and use thereof
CN108543108A (en) * 2018-05-02 2018-09-18 山东虎力机械有限公司 A kind of department of anesthesia often uses sterilizing sponge
CN112891997A (en) * 2021-01-29 2021-06-04 中国科学院长春应用化学研究所 Emulsion separation material and preparation method thereof

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101912634B (en) * 2010-08-06 2013-09-25 华南理工大学 Method for preparing nanosilver/nano silicon dioxide-containing antibacterial biological dressing
CN101912634A (en) * 2010-08-06 2010-12-15 华南理工大学 Method for preparing nanosilver/nano silicon dioxide-containing antibacterial biological dressing
CN101954115A (en) * 2010-10-22 2011-01-26 佘振定 Medical antibacterial sponge dressing and preparation method thereof
CN101967254A (en) * 2010-10-22 2011-02-09 佘振定 Medicinal microporous sponge and preparation method thereof
CN101967254B (en) * 2010-10-22 2012-10-17 深圳齐康医疗器械有限公司 Medicinal microporous sponge and preparation method thereof
CN102871953A (en) * 2012-10-09 2013-01-16 姜志银 Super-absorbent adsorption suppository
CN104558988A (en) * 2013-10-11 2015-04-29 上海工程技术大学 High-elasticity strong-hydroscopicity chitosan sponge allowing normal-temperature drying and preparation method thereof
CN104497348B (en) * 2014-12-31 2018-10-26 武汉奥绿新生物科技股份有限公司 A kind of submissiveization Processes and apparatus of poly- polysaccharide freeze-drying sponge dressing
CN104497348A (en) * 2014-12-31 2015-04-08 武汉奥绿新生物科技有限公司 Softening technology and equipment for polysaccharides lyophilized sponge dressing
CN105194713A (en) * 2015-09-08 2015-12-30 广州润虹医药科技有限公司 Medical sponge with anti-microbial, heal-promoting and anti-adhesion functions and preparation method thereof
CN105999365A (en) * 2016-07-26 2016-10-12 四川艾医生医疗科技有限公司 Functional nasal cavity hemostatic material and preparation method thereof
CN105999365B (en) * 2016-07-26 2019-05-03 四川艾医生医疗科技有限公司 A kind of effect type nose cavity hemostatic material and preparation method thereof
WO2018113147A1 (en) * 2016-12-20 2018-06-28 欣乐加生物科技有限公司 Dry gel sponge of super water-absorbent polymer hydrogel, preparation method therefor and use thereof
CN107224603A (en) * 2017-05-31 2017-10-03 武汉医佳宝生物材料有限公司 A kind of Medical negative pressure drainage composite foam material and preparation method thereof
CN107216479A (en) * 2017-07-26 2017-09-29 河北科技大学 A kind of preparation method of polyvinyl formal water suction foams
CN107722342B (en) * 2017-10-13 2021-01-08 中国科学院长春应用化学研究所 Porous antibacterial material and preparation method thereof
CN107722342A (en) * 2017-10-13 2018-02-23 中国科学院长春应用化学研究所 A kind of porous anti-biotic material and preparation method thereof
CN108543108A (en) * 2018-05-02 2018-09-18 山东虎力机械有限公司 A kind of department of anesthesia often uses sterilizing sponge
CN108543108B (en) * 2018-05-02 2020-12-25 青岛大学附属医院 Common sterilization sponge for anesthesia department
CN112891997A (en) * 2021-01-29 2021-06-04 中国科学院长春应用化学研究所 Emulsion separation material and preparation method thereof
CN112891997B (en) * 2021-01-29 2021-11-09 中国科学院长春应用化学研究所 Emulsion separation material and preparation method thereof

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