CN104771780B - Preparation method for polymeric hydrogel for dressing - Google Patents
Preparation method for polymeric hydrogel for dressing Download PDFInfo
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- CN104771780B CN104771780B CN201510163532.1A CN201510163532A CN104771780B CN 104771780 B CN104771780 B CN 104771780B CN 201510163532 A CN201510163532 A CN 201510163532A CN 104771780 B CN104771780 B CN 104771780B
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Abstract
The invention provides a polymeric hydrogel for dressing and a preparation method of the polymeric hydrogel, belonging to the fields of radiation chemical and biomedical polymeric materials. The polymeric hydrogel is prepared from gelatin, sodium carboxymethylcellulose, gulcomannan, water-soluble chitosan, polyglutamic acid, hyaluronic acid and the like which are good in biocompatibility through blending, hot orientation and packaging; by controlling the temperature of hot orientation as well as orientation force and orientation time, the mechanical strength of the hydrogel is enhanced, and through high energy ray irradiation crosslinking, a regular aggregation structure obtained from the orientation is further immobilized and enhanced so as to synthesize high-strength dressing. The hydrogel disclosed by the invention is good in physicochemical and biological properties, high in tensile strength and good in transparency, and the hydrogel is relatively good in antibacterial and healing-promoting effects when applied to dressing. The polymeric hydrogel for dressing disclosed by the invention not requires an adhesive, a non-woven fabric or other reinforcing layers during preparing, and the polymeric hydrogel is simple in process and low in energy consumption; and the polymeric hydrogel can achieve sterilization and disinfection when radiating, and the polymeric hydrogel can reduce production cost and bring about benefit for production in a large scale.
Description
Technical field
The present invention relates to a kind of preparation method of the macromolecule hydrogel for dressing, belongs to radiation chemistry and bio-medical
Polymeric material field.
Background technology
Hydrogel with the three-dimensional crosslinked network structure of hydrophilic polymer as skeleton, such that it is able to absorbing in a large number and keeping water
Divide in solvent swelling state and do not dissolve, be integrated with the properties such as water suction, water conservation, slow release, be the excellent functional material of a class, it is special
Moist medical dressing Shi Yongyu not be developed.The aerogel dressing not only permeable oxygen flow of soft and transparent, is absorbing wound fluid, is keeping
Wound surface is moistened with while debridement, can accelerate wound healing.Find from the inventions of Winter in 1962 " wet method therapy " closed wet
After moistening environment speed of wound healing faster, various moist dressings are had been developed, but is considered as most connecing the characteristics of aerogel dressing
The requirement of nearly ideal dressing.
Aerogel dressing is mainly with synthesis or natural polymer as raw material.Synthesis macromolecular structure determines, easy to process, power
Better performances are learned, but its biocompatibility is poor, available types are limited and itself or catabolite easily cause environmental pollution.It is natural
High molecular biocompatibility is preferable, wide material sources, with low cost and biodegradable, catabolite safety, while there is also
The shortcomings of mechanical strength is poor.Therefore need to improve the method that natural polymer prepares aerogel dressing, strengthen the machinery of dressing
Intensity.
The preparation method of aerogel dressing mainly has the physical methods such as blending, freeze thawing, spinning and grafting, copolymerization, radiation
The chemical methodes such as crosslinking.The aerogel dressing prepared using physical method is opaque, is unfavorable for wound observation.Using graft copolymerization
Need using harmful substances such as cross-linking agent, initiator, toxic monomers etc. chemical method, micro residue can all cause application risk urgency
Increase severely and add.The radiation cross-linking process of the inventions such as Rosiak in 1986 is the most commonly used, and radiation cross-linking process has that preparation condition is gentle, process
It is simple and easy to control, do not use toxic cross-linking agents, products pure, crosslinking with radiation and disinfection while the advantages of carrying out.But radiation method
For the natural polymer Degradation of most of single raw material is more than crosslinked action, obtained mechanical strength is poor.
" a kind of can be used as temperature-sensitive hydrogel of nourishing pack and preparation method thereof " be disclosed such as CN102949583A, using natural polymer
Hydrogel transparent flexible that sub- raw material is prepared by radiation method but mechanical strength is not enough, it is uncomfortable to be used as dressing.CN103071181A
Disclose " a kind of hydrogel and its production and use ", the natural polymer loading active constituents of medicine is irradiated to be obtained
Hydrogel, to prevent irradiation-induced degradation from employing oxygen free condition, technological requirement is higher and gel fraction of gained hydrogel is still low
In 45%.
To solve the problems, such as that radiation method prepares that aerogel dressing intensity is poor, Many researchers have done substantial amounts of trial work
Make.Mainly there are following several thinkings：
Compound preparation method-adopt more non-woven fabrics or ventilated membrane compound preparation bonding with hydrogel, medical adhesive etc.
Form.As CN102284081A discloses a kind of composite aquogel dressing containing nonwoven layer and the hydrogel layer being provided thereon,
Hydrogel layer containing water-soluble polymer and monomer and water-solubility chitosan derivative, are made using electron accelerator irradiation crosslinking.
Though composite bed enhances the mechanical strength of hydrogel to a certain extent, the non-woven fabrics adopted by which are opaque, are unfavorable for observation
Wound healing situation, and the medical adhesive used to strengthen the associativity of compound interlayer causes preparation process increasingly complex.
CN1121876C discloses " hydrogel compounded dressing for wound and its radiation synthesis process ", what the dressing was synthesized by crosslinking with radiation
Hydrogel is constituted with transparent polymeric film, and with good transparency, breathability and water penetration, but its water absorption rate is only 200-
400%.CN101337086A discloses " a kind of aerogel dressing and preparation method thereof ", is composited by two-layer hydrogel, up and down
Layer is respectively adopted radiation method and prepared by freeze thawing radiation method, and with the excellent transparency and absorbent, but 6 intensity of its freeze thawing are only
Up to 11kPa, and preparation process is complicated, and production is difficult to scale.
Blending type preparation method-by natural polymer and the polymer blended rear cross-linking radiation of synthesis.CN103480034A is public
Cloth " cross-linking radiation shitosan/gelatin/polyvinyl alcohol hydrogel dressing and its preparation method and application ", the natural polymer of employing
Son is shitosan and gelatin, and synthesis macromolecule is polyvinyl alcohol, and aerogel dressing prepared by crosslinking by radiation has antiinflammatory, promotees to heal
And the advantages of good biocompatibility, but imbibition ability is not strong, and polyvinyl alcohol is difficult to biodegradation and causes serious environmental problem.
CN1320931C and CN101664562A there is also same problem, and it is poisonous that CN1320931C additionally there are wetting agent plasticizer etc.
Hazard residue.CN100389145C discloses " water gel containing natural high molecule and its radiation preparation method ", using various days
So macromolecule or derivatives thereof mixes with macromolecule, inorganic filler, crosslinking sensitive agent etc. is synthesized, and crosslinking by radiation prepares water-setting
Glue, compound nonwoven cloth or ventilated membrane can be used for wound dressing, but residual raw materials, by-product and catabolite can be to its biofacies
Capacitive is impacted.CN103520767A discloses " a kind of antibacterial heal-promoting aerogel dressing and preparation method thereof ", main component
For water soluble polymer, with pseudoplastic functional polymer, antibacterial and water, solidification irradiation sterilization obtain it is transparent it is pure,
Good biocompatibility, antibacterial aerogel dressing evident in efficacy, but its imbibition ability is limited, and pliability is not obvious.
Method conjunction type preparation method-respectively freeze-thaw method, infusion process etc. are combined with irradiation method.As in CN101244286A
Aerogel dressing prepared by thaw cycle method is freezed after described first irradiation, as predose is solution shape, it is impossible to one-shot forming,
Freeze thaw cycle to remain a need for aseptically processing after irradiation, and it is time-consuming longer, it is unfavorable for the raising of production efficiency.
CN103044694A is disclosed " a kind of preparation method of bacteria cellulose/polyvinyl alcohol composite aquogel ", is made using first dipping
Polyvinyl alcohol is immersed inside bacteria cellulose aquagel, then Jing deaerations, processed, and irradiation obtains composite aquogel, technique
Process needs repeatedly repeatedly high-temperature wash, rinses, time and effort consuming.
The content of the invention
The invention solves the problems that another technical problem be to provide a kind of preparation method of the macromolecule hydrogel for dressing.
The preparation method of the macromolecule hydrogel for dressing of the present invention, is comprised the following steps successively：
A). according to the component composition of macromolecule hydrogel with ratio by gelatin, sodium carboxymethyl cellulose, glucomannoglycan, water
Soluble chitosan, polyglutamic acid, hyaluronic acid are dissolved in water, agitated to homogeneous mixture；
B). the homogeneous mixture obtained by step a is carried out into hot orientation process, temperature is 10 C ~ 100 C, and dipole-dipole force is 3
MPa ~ 15MPa, time are 0.1 min ~ 60min；
C). the flaky material obtained by step b is encapsulated and the cross-linking radiation under high-energy ray, is 0.5kGy in absorbed dose
Crosslinking synthesis hydrogel during ~ 250kGy；
The component composition of the macromolecule hydrogel is as follows with percentage by weight：
Gelatin 3% ~ 40%；
Sodium carboxymethyl cellulose 0.1% ~ 15%；
Glucomannoglycan 0.1% ~ 5%；
Water-soluble chitosan 0.1% ~ 5%；
Polyglutamic acid 0.1% ~ 15%；
Hyaluronic acid 0.1% ~ 12%；
Water 40% ~ 96.5%.
Above steps is all carried out at ambient temperature and pressure.
The content of the gelatin is 10% ~ 30%.
The content of the sodium carboxymethyl cellulose is 0.2% ~ 10%.
The content of the polyglutamic acid is 3% ~ 12%.
The water is deionized water.
In above-mentioned composition, gelatin can form heat-convertible gel, high-temperature digestion beneficial to mixing, room temperature congeal beneficial to into
Type, processing, and cause hydrogel that there is certain elasticity and toughness；Sodium carboxymethyl cellulose, glucomannoglycan have thickening froth breaking
With the effect of water conservation；Water-soluble chitosan is used as antibacterial heal-promoting composition；Polyglutamic acid has good biological moisturizing with hyaluronic acid
Property.The combination of these components and the above-mentioned percentage range of each component, be by lot of experiments determine, combinations thereof and
Percentage range makes the dressing that subject hydrogel compositions are formed have water absorption, the transparency and the enhanced association of cross-linking radiation
Same effect.
The present invention the macromolecule hydrogel for dressing by water soluble polymer Jing aqueous solutions blending, heat orientation, encapsulation,
Cross-linking radiation is prepared from.
Using aligned acquisition is strengthened, aligned be that hot-stretch or heat extend to described high-intensity performance, enhancement bar
Part includes temperature, dipole-dipole force and orientation control etc..
The high-energy ray type that cross-linking radiation is adopted under described high-energy ray is for gamma ray, electron beam, ion beam, purple
One or more in outside line.
The present invention compared with prior art, has the advantage that：
As the aerogel dressing of present invention offer is with biological source macromolecule as raw material, nontoxic, good biocompatibility,
And can be with biodegradation, with very high environment friendly.And without the plasticizers such as glycerol, glycerol, Polyethylene Glycol, addition
Agent, it is to avoid the side effect that the dissolution of such material is caused.
The tensile strength of the hydrogel that the present invention is provided is big and the transparency is good, is not required to reuse adhesive or nothing for dressing
Spin the enhancement layer such as cloth, it is to avoid complicated preparation process, and be beneficial to wound observation.
The biocompatibility of the hydrogel that the present invention is provided is good, has antibacterial heal-promoting effect for dressing.
The hydrogel that the present invention is provided has good physicochemical property, and such as gel fraction is big, absorbency is strong, elongation at break
Greatly, good permeability, pH are moderate etc..
The method combined with cross-linking radiation using heat orientation by the hydrogel that the present invention is provided, preparation process is simple, energy consumption are low,
Sterilizing is realized simultaneously in irradiation, reduce production cost.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply in a scope.
Embodiment 1
At normal temperatures and pressures, soluble in water by each component mixing specified in table 1 below respectively, preparation uniformly mixes
Thing, pours the mixture into the mould for being covered with plastic foil, and 25 C extend and are orientated, and dipole-dipole force 12MPa, orientation 60min are completed
After cut pack sealing, with the sterilizing of Co-60 sources accumulated doses 100kGy cross-linking radiation.Gained hydrogel carries out every test, tests
As a result it is listed in table 2.
Each component ratio of the table 1 for embodiment.
Technological parameter and test result of the table 2 for corresponding embodiment.
Embodiment 2
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 3
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 4
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, but added with electronics
Fast device instead of Co-60 sources, and technological parameter and test result are listed in table 2.
Embodiment 5
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 6
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 7
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 8
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 9
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 10
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
Embodiment 11
At normal temperatures and pressures, the method for repeating embodiment 1 by each component content listed in table 1 below, lists in table 2
Technological parameter and test result.
The appearance transparent of each embodiment hydrogel in table 2 below, tensile strength and water absorbing properties it is excellent, good biocompatibility,
No matter on single performance, or in combination property, the hydrogel composition of the present invention is all significantly carried better than documents
For hydrogel composition, and the hydrogel that the present invention is provided can be with biodegradation, preparation process is simple, and irradiation is realized killing simultaneously
Bacterium is sterilized, low production cost.
Table 1
Table 2
Claims (6)
1. a kind of preparation method of the macromolecule hydrogel for dressing, it is characterised in that comprise the following steps successively：
A). according to the component composition of macromolecule hydrogel with ratio by gelatin, sodium carboxymethyl cellulose, glucomannoglycan, water solublity
Shitosan, polyglutamic acid, hyaluronic acid are dissolved in water, agitated to homogeneous mixture；
B). the homogeneous mixture obtained by step a is carried out into hot orientation process, temperature is 10 C ~ 100 C, and dipole-dipole force is 3 MPa
~ 15MPa, time are 0.1 min ~ 60min；
C). by obtained by step b flaky material encapsulation and under high-energy ray cross-linking radiation, absorbed dose be 0.5kGy ~
Crosslinking synthesis hydrogel during 250kGy；
The component composition of the macromolecule hydrogel is as follows with percentage by weight：
Gelatin 3% ~ 40%；
Sodium carboxymethyl cellulose 0.1% ~ 15%；
Glucomannoglycan 0.1% ~ 5%；
Water-soluble chitosan 0.1% ~ 5%；
Polyglutamic acid 0.1% ~ 15%；
Hyaluronic acid 0.1% ~ 12%；
Water 40% ~ 96.5%.
2. the preparation method of macromolecule hydrogel according to claim 1, it is characterised in that：The content of the gelatin is
10%~30%。
3. the preparation method of macromolecule hydrogel according to claim 1, it is characterised in that：The sodium carboxymethyl cellulose
Content be 0.2% ~ 10%.
4. the preparation method of macromolecule hydrogel according to claim 1, it is characterised in that：The content of the polyglutamic acid
For 3% ~ 12%.
5. the preparation method of macromolecule hydrogel according to claim 1, it is characterised in that：The water is deionized water.
6. the preparation method of macromolecule hydrogel according to claim 1, it is characterised in that：Spoke under described high-energy ray
According to the high-energy ray type that adopts of crosslinking for one or more in gamma ray, electron beam, ion beam, ultraviolet；It is above-mentioned each
Step is all carried out at ambient temperature and pressure.
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| CN105268015B (en) * | 2015-11-11 | 2019-04-30 | 南开大学 | A kind of antibiotic property hydrogel composite material and preparation method thereof |
| CN106039393A (en) * | 2016-06-16 | 2016-10-26 | 湖州科达化工燃料有限公司 | Anti-inflection skin adhesive |
| CN107335143B (en) * | 2016-12-29 | 2020-07-28 | 吴国宪 | Wearable facial low frequency electromagnetism physiotherapy face guard based on trace living beings electromagnetic stimulation |
| CN106964303A (en) * | 2017-04-21 | 2017-07-21 | 北京健康广济生物技术有限公司 | Hydrogel production technology and device |
| CN107814981B (en) * | 2017-11-09 | 2020-09-22 | 四川艾医生医疗科技有限公司 | Chitosan hydrogel dressing and preparation method thereof |
| CN108841318A (en) * | 2018-07-12 | 2018-11-20 | 中国科学院海洋研究所 | A kind of selfreparing aquagel anticorrosive paint and its synthetic method |
| CN109354702A (en) * | 2018-10-23 | 2019-02-19 | 东北农业大学 | High swelling property bean dregs Process for preparing hydrogels |
| CN113214507B (en) * | 2021-05-12 | 2022-06-10 | 中国医学科学院生物医学工程研究所 | Preparation method of antibacterial glycopeptide hydrogel |
| CN113521380B (en) * | 2021-06-30 | 2022-12-13 | 东南大学 | Rapid polymerization hydrogel material and preparation method and application thereof |
| CN114736398B (en) * | 2022-05-17 | 2024-02-06 | 西安建筑科技大学 | Copper nanoparticle-clove oil double-layer antibacterial hydrogel and preparation method thereof |
| CN117258037A (en) * | 2023-08-25 | 2023-12-22 | 陕西佰傲再生医学有限公司 | Sodium hyaluronate facial filler and preparation method thereof |
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| FR2921675B1 (en) * | 2007-09-28 | 2010-03-19 | Univ Claude Bernard Lyon | HYALURONIC ACID FILAMENT AND PROCESS FOR OBTAINING SAME |
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| CN103013106A (en) * | 2013-01-10 | 2013-04-03 | 天津工业大学 | Preparation method of gamma-polyglutamic acid/Pulullan composite hydrogel |
| CN103585670A (en) * | 2013-10-17 | 2014-02-19 | 合肥博太医药生物技术发展有限公司 | Plant glucomannan silicone dressing as well as preparation method and application thereof |
| CN103751833A (en) * | 2014-01-28 | 2014-04-30 | 北京百利康生化有限公司 | Medical antibacterial wound dressing and preparation method thereof |
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