CN101693121B - Method for preparing hydrogel dressing with half interpenetrating network structure and application - Google Patents
Method for preparing hydrogel dressing with half interpenetrating network structure and application Download PDFInfo
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Abstract
The invention provides a method for preparing a hydrogel dressing with a half interpenetrating network structure. The hydrogel dressing with the half interpenetrating network structure is a gel dressing which takes gel with the half interpenetrating network structure as a framework, wherein the gel with the half interpenetrating network structure is formed by a natural linear high molecular material with favorable biologic compatibility and a polyacrylamide-polyoxyethylene high molecular three-dimensional network structure which is artificially synthesized. The invention integrates natural high molecular materials and synthetic high molecular materials into a gel system organically by the high molecular half interpenetrating network structure; except for good adhesion property, bacterium isolation and humidity preservation of a wound face, the materials can promote the healing of the skin of the wound face, have excellent adhesion property and accompanying property of the wound face and stronger water-absorption and water-perservation capacities and are more beneficial to promoting the healing of the wound face; and because of a framework structure in a three-dimensional gel film, a polyethylene glycol chain segment in the framework structure has very large hydratation capability, a gel film is easily removed from the wound face without damaging the already recovered wound face; and the hydrogel dressing with the half interpenetrating network structure can be used as a coverage dressing of a temporary wound face for promoting the healing of the skin of the wound face.
Description
Technical field
The invention belongs to the technical field that medical material is made, relate to the method for preparing of a kind of natural polymer/synthetic high polymer hydrogel dressing with half interpenetrating network structure.
Background technology
Often there is the insufficient problem of skin donor part in patient for needing the large tracts of land skin-grafting, need could cure successfully through repeatedly transplanting.For the large tracts of land skin-grafting patient that can not realize self-skin transplant in a short time; In the process of waiting for self-skin transplant; Because the wound surface long term exposure very easily causes patient's body fluid to run off in a large number, the wound surface severe infections; Cause heavy physiology, psychology and financial burden to the patient, even possibly produce severe complication and cause individual death.Therefore, in large tracts of land skin-grafting patient treatment clinical course, it is indispensable that temporary wound-surface cover uses at present.Temporary dressing is kept the wound surface cleaning and is prolonged irreplaceable effect on patient's life span before self-skin transplant, and make it is one of research focus of biomedical materials field always.
Macromolecular material is the material base of novel skin dressing development on the Modern Significance, and its function of the structures shape of material, therefore, the dressing for skin of development of new must design the macromolecular material with suitable construction.The functional components of the temporary dressing of synthesis type that uses clinically now generally all is these several kinds of macromolecular materials such as partial cross-linked polyacrylamide, polyurethane, polyvinyl alcohol; These materials except adhesion is good, isolate bacteria and maintenance wound surface moistening, do not have other function.And natural collagen, hyaluronic acid, chitosan and alginic acid etc. all have excellent biological compatibility, and research shows that these natural materials can both promote the healing of wound surface skin in varying degrees.If with the macromolecule of synthesis type and natural macromolecule organic assembling, so novel dressing is with the advantage that has the two simultaneously.
According to two kinds of high molecular architectural features; We think that structure macromolecule half interpenetrating network structure hydrogel can be with the two organic assembling; Synthesis type macromolecule such as polyacrylamide provide the skeleton of three-dimensional net structure in this macromolecule inierpeneirating network structure; And natural molecule such as hyaluronic acid or chitosan etc. by machinery seal between the polyacrylamide strand, its activity can remain unchanged.
Summary of the invention
The method for preparing that the purpose of this invention is to provide a kind of hydrogel dressing with half interpenetrating network structure; The gel that is the half interpenetrating network structure that forms of the polyacrylamide-polyoxyethylene polymer three-dimensional network structure with good natural linear polymeric material of biocompatibility and synthetic is as skeleton, as a kind of novel gel dressing.This method for preparing realizes through following steps:
(1) after methylbenzene azeotropic dewaters, be dissolved in hydroxyl carbowax in the dry tetrahydrofuran; Under ice bath and nitrogen protection, slowly drip acryloyl chloride (acryloyl chloride: the molar ratio of ethylene glycol is 3: 1); Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night.The elimination solid, the evaporate to dryness clear liquid, in the dichloromethane that crude product is dissolved in, with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent;
(2) one or more of acrylamide and natural macromolecular material (like glucosan hyaluronic acid, chitosan, collagen, carrageenan, gelatin or agar) are dissolved in the aqueous solution, add the Polyethylene Glycol double methacrylate cross-linking agent that step (1) obtains simultaneously, with persulfate-N; N; N ', N '-tetramethylethylenediamine (N, N; N ' N '-tetramethylethylenediamine; TMED) redox system initiated polymerization can obtain difform gel through in difform mould, carrying out polymerization, and wherein solid content is 10～30%.
Perhaps can also be (3): acrylamide and one or more natural macromolecular materials (glucosan, hyaluronic acid, chitosan, collagen, carrageenan, gelatin or agar) are dissolved in the aqueous solution; Add the Polyethylene Glycol double methacrylate cross-linking agent that step (1) obtains simultaneously, under the room temperature
60Co gamma-rays or high-power electron beam x ray irradiation x are crosslinked, can obtain difform gel through in difform mould, carrying out polymerization, and wherein solid content is 10～30%.
The molecular weight from 100 to 10000 of the hydroxyl carbowax described in the step of the present invention (1), wherein optimum molecular weight is 1000～5000.
Natural polymer described in step of the present invention (2) and (3) is linear polymeric, is commercial product all, and the corresponding complete series product of every kind of macromolecule used among the present invention all is raw material sources of the present invention.
The described redox initiation condition of step of the present invention (2) is that ultraviolet causes and thermal initiation, and wherein the condition of thermal initiation is 60～120 degrees centigrade.
The mass ratio of acrylamide described in step of the present invention (2) and (3) and natural polymer is 0.1: 1～10: 1, and wherein optimal proportion is 0.3: 1～5: 1.
Persulfate-N described in the step of the present invention (2), N, N ', N '-tetramethylethylenediamine (N, N, N ' N '-tetramethylethylenediamine, TMED) concentration of redox system is 0.01～1wt-%, preferred concentration is 0.1wt-%.
In the step of the present invention (3)
60Co gamma-rays or high-power electron beam x ray irradiation x dosage are 10～80kGy.
Another object of the present invention provides prepared hydrogel dressing with half interpenetrating network structure and covers the application in the dressing at the temporary wound surface that promotes the wound surface skin healing.
The present invention utilizes the macromolecule half interpenetrating network structure with in a natural polymer and synthetic high polymer organic combination to a gel systems, these materials except adhesion is good, isolate bacteria and maintenance wound surface moistening, these materials can promote the healing of wound surface skin.Material with this structure covers dressing with the temporary wound surface of present use and compares, owing to have the lower degree of cross linking, therefore will have excellent wound surface adhesion and retinue property, and its water-absorbing-retaining ability is stronger, more helps promoting wound healing; Because be that framing structure in the three dimensional gel thin film is polyacrylamide-polyethylene glycol structures, the Polyethylene Glycol segment has great hydration capability in this structure, make gel film easy when wound surface is removed, can not damage the wound surface that has recovered.
Description of drawings
Fig. 1 is the acrylamide triggered and Polyethylene Glycol double methacrylate polymerization formation PAAG sketch map of free radical.
Fig. 2 is that free radical polymerization forms polyacrylamide Polyethylene Glycol and glucosan half interpenetrating network structure gel rubber material sketch map.
The specific embodiment
The present invention combines accompanying drawing and embodiment to be further described.Embodiments of the invention are just explained characteristic of the present invention for better, and not exclusively comprise the content of being protected of this patent.
Embodiment one: the preparation of Polyethylene Glycol double methacrylate cross-linking agent
With the molecular weight of 10g is that 100 hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran of 100g; Under ice bath and nitrogen protection, slowly drip acryloyl chloride (3 times of Polyethylene Glycol amount of substances); Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night.The elimination solid, the evaporate to dryness clear liquid is dissolved in crude product in a certain amount of dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent.
Embodiment two: the preparation of Polyethylene Glycol double methacrylate cross-linking agent
With the molecular weight of 10g is that 1000 hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran of 100g; Under ice bath and nitrogen protection, slowly drip acryloyl chloride (3 times of Polyethylene Glycol amount of substances); Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night.The elimination solid, the evaporate to dryness clear liquid is dissolved in crude product in a certain amount of dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent.
Embodiment three: the preparation of Polyethylene Glycol double methacrylate cross-linking agent
With the molecular weight of 10g is that 5000 hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran of 100g; Under ice bath and nitrogen protection, slowly drip acryloyl chloride (3 times of Polyethylene Glycol amount of substances); Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night.The elimination solid, the evaporate to dryness clear liquid is dissolved in crude product in a certain amount of dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent.
Embodiment four: the preparation of Polyethylene Glycol double methacrylate cross-linking agent
With the molecular weight of 10g is that 10000 hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran of 100g; Under ice bath and nitrogen protection, slowly drip acryloyl chloride (3 times of Polyethylene Glycol amount of substances); Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night.The elimination solid, the evaporate to dryness clear liquid is dissolved in crude product in a certain amount of dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent.
Embodiment five: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.01g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system ultraviolet-initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment six: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.01g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) 60 degrees centigrade of initiated polymerizations of redox system, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment seven: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.01g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) 120 degrees centigrade of initiated polymerizations of redox system, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment eight: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.01g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment nine: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment ten: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 1g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 11: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 3g and the glucosan of 10g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 12: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 10g and the glucosan of 2g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 13: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 10g and the glucosan of 1g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.02g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 14: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 10g and the glucosan of 2g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.1g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 15: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 10g and the glucosan of 2g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 0.5g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 16: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
The acrylamide of 10g and the glucosan of 2g are dissolved in the aqueous solution, add the cross-linking agent Polyethylene Glycol double methacrylate 1g of molecular weight 5000 simultaneously, with 0.1g persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, polyacrylamide-Polyethylene Glycol course of reaction is referring to Fig. 1.Can obtain difform gel through in difform mould, carrying out polymerization, the gel formation process is referring to Fig. 2.
Embodiment 17: the preparation of hyaluronic acid-poly acrylamide Polyethylene Glycol gel rubber system
A certain amount of acrylamide and hyaluronic acid are dissolved in the aqueous solution, add cross-linking agent Polyethylene Glycol double methacrylate simultaneously, with persulfate-N; N, N ', N '-tetramethylethylenediamine (N; N; N ' N '-tetramethylethylenediamine, TMED) redox system initiated polymerization, the selection of course of reaction material preparation and various amounts can be with reference to embodiment one～embodiment 14.
Embodiment 18: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
A certain amount of acrylamide and glucosan being dissolved in the aqueous solution, add cross-linking agent Polyethylene Glycol double methacrylate simultaneously, is under the 10kGy room temperature with dosage
60Co gamma-rays or high-power electron beam x ray irradiation x are crosslinked.Can obtain difform gel through in difform mould, carrying out polymerization.The selection of the various amounts of course of reaction can be with reference to embodiment one～embodiment 14.
Embodiment 19: glucosan-polyacrylamide Polyethylene Glycol gel rubber system preparation
A certain amount of acrylamide and glucosan being dissolved in the aqueous solution, add cross-linking agent Polyethylene Glycol double methacrylate simultaneously, is under the 800kGy room temperature with dosage
60Co gamma-rays or high-power electron beam x ray irradiation x are crosslinked.Can obtain difform gel through in difform mould, carrying out polymerization.The selection of the various amounts of course of reaction can be with reference to embodiment one～embodiment 14.
Embodiment 20: the preparation of hyaluronic acid-poly acrylamide Polyethylene Glycol gel rubber system
A certain amount of acrylamide and hyaluronic acid are dissolved in the aqueous solution, add cross-linking agent Polyethylene Glycol double methacrylate simultaneously, under room temperature
60Co gamma-rays or high-power electron beam x ray irradiation x are crosslinked.Can obtain difform gel through in difform mould, carrying out polymerization.The selection of the various amounts of course of reaction can be with reference to embodiment 15;
60The dosage of Co gamma-rays or high-power electron beam x ray irradiation x is with reference to embodiment 16～embodiment 17.
Embodiment 21: the physicochemical property test of semi-interpenetrating network gel material
Water absorbing capacity test: exsiccant gel film is positioned in the pure water, after the saturated absorption, weighs and, wherein C=W in the desciccator diaphragm anharmonic ratio
2/ W
1* 100% (C: inhale anharmonic ratio, W1: dry weight, W2: saturated heavy).The water that can adsorb 15～40 times of own wts of this material.
Proteoglycan material absorbability is tested: different desciccator diaphragms is positioned over respectively (wherein test fluid is by milk in the test fluid of variable concentrations; Ovum Gallus domesticus album, cheese and hyclone equivalent are dissolved in the 0.15M sodium chloride solution, form 10% solid content concentration); After the saturated absorption; Gel film is taken out from solution, with filter paper blot surface moisture and weigh (W2) and with desciccator diaphragm heavy (W1) relatively, anharmonic ratio is inhaled in test; Simultaneously, with the gel film after the saturated absorption dry (W3), the heavy difference heavy of more saturated desciccator diaphragm with desciccator diaphragm.This material can adsorb the material of own wt more than 50 times.
Embodiment 22: angle conjunctiva stimulation test
Japan large ear rabbit, male and female half and half are divided into antiseptic gauze, polyacrylamide Polyethylene Glycol-polydextran gel group, polyacrylamide Polyethylene Glycol-hyaluronic acid derivatives group, 8 every group at random.Lagophthalmos gives the gel dressing leachate at random or 0.01nmol/L PBS compares (matched group), and every day, administration was 1 time, and 7d continues to observe for 2 weeks continuously.2 all interior lagophthalmos angles conjunctivas have or not hyperemia, edema and ulcer to take place after observing administration; Change with slit lamp examination corneal transparence and iris texture.Judge that being tried thing stimulates degree, wherein average 0～3 is divided into nonirritant; 4～8 are divided into slight zest; 9～12 are divided into the moderate zest; 13～16 are divided into strong and stimulating.Experiment shows, such gel rubber material nonirritant.
Embodiment 23: the muscular irritation experiment
Japan large ear rabbit; Male; Inject each 4 place of antiseptic gauze, polyacrylamide Polyethylene Glycol-polydextran gel group, polyacrylamide Polyethylene Glycol-hyaluronic acid derivatives group dressing leachate and 0.01nmol/L PBS at rabbit quadriceps femoris middle part at random; Animal is put to death in the air injection behind the 48h, and the perusal quadriceps femoris has or not hyperemia, edema or necrosis.4 point of observation overall score＜10 can be judged as avirulence (each point of observation scoring differs and is no more than 2 fens).Result of the test shows, such gel rubber material avirulence.
Embodiment 24: dressing is to the influence (rate, time) of wound healing
Choice of animal models: spontaneous recovery does not need special processing because wound surface damage kicks the beam rapidly, and the wound surface damage is overweight then must make skin graft otherwise can't heal, and selects for use dark II degree skin scald model as estimating the animal model that dressing influences wound healing for this reason.
Be in brief; Male Wistar rat; Random packet; Comprise normal healing group, gauze conventional treatment group, Omiderm group (the external high like product of a kind of clinical frequency of utilization), polyacrylamide Polyethylene Glycol-polydextran gel group, polyacrylamide Polyethylene Glycol-hyaluronic acid derivatives group, put mutually when each group is observed to hindering back 3,7,14,21d, put 10 animals when per mutually for every group.Rat back is with 8% sodium sulfide loss of thick fluid hair, and 24h is after the abdominal cavity gives pentobarbital sodium, anaesthetizes successfully the back and scalds with 80 ℃ of water-baths and caused rat back 10% dark II degree skin scald (sick inspection section confirmation) in 15 seconds, and wound is after the abdominal cavity gives 5ml normal saline.Except that the normal healing group, each group is used corresponding dressing flap coverage respectively.Each puts the wound healing rate of surveying when confirming mutually to hinder the back, earlier wound surface is traced on onionskin, again as template, the uniform hard paper of quality is cut into onesize, weighs in the balance then heavily, representes wound surface area size indirectly with hard paper weight.Be calculated as follows the wound healing rate: wound healing rate (%)=(original wound surface area-the wound surface area does not heal)/original wound surface area.Pathologic finding is understood the wound healing quality, and confirms healing time according to the wound healing situation.Result of the test shows; Polyacrylamide Polyethylene Glycol-polydextran gel group, polyacrylamide Polyethylene Glycol-hyaluronic acid derivatives group; All be superior to normal healing group, gauze conventional treatment group, Omiderm group on recovery time and aspect the wound healing rate two at wound surface, wherein polyacrylamide Polyethylene Glycol-polydextran gel group compare with polyacrylamide Polyethylene Glycol-hyaluronic acid derivatives group poor slightly.
Claims (8)
1. the method for preparing of a hydrogel dressing with half interpenetrating network structure, realize through following steps:
(1) hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran, under ice bath and nitrogen protection, slowly drips acryloyl chloride, acryloyl chloride: the mol ratio of Polyethylene Glycol is 3: 1; Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night, the elimination solid; The evaporate to dryness clear liquid; Crude product is dissolved in the dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent;
(2) acrylamide and one or more natural macromolecular materials are dissolved in the aqueous solution; Add the Polyethylene Glycol double methacrylate cross-linking agent that step (1) obtains simultaneously, with persulfate-N, N; N '; N '-tetramethylethylenediamine redox system initiated polymerization can obtain difform gel through in difform mould, carrying out polymerization, and wherein solid content is 10～30%;
The described natural polymer of step (2) is selected one or more in glucosan, hyaluronic acid, chitosan, collagen, carrageenan, gelatin or the agar for use.
2. the method for preparing of a hydrogel dressing with half interpenetrating network structure, realize through following steps:
(1) hydroxyl carbowax is dissolved in after methylbenzene azeotropic dewaters in the dry tetrahydrofuran, under ice bath and nitrogen protection, slowly drips acryloyl chloride, acryloyl chloride: the mol ratio of Polyethylene Glycol is 3: 1; Drip off the recession deicing and bathe, under nitrogen protection, react and spend the night, the elimination solid; The evaporate to dryness clear liquid; Crude product is dissolved in the dichloromethane, and with saturated nacl aqueous solution washing three times, the deposition that adds diethyl ether after organic facies concentrates obtains Polyethylene Glycol double methacrylate cross-linking agent;
(2) acrylamide and one or more natural macromolecular materials are dissolved in the aqueous solution, add the Polyethylene Glycol double methacrylate cross-linking agent that step (1) obtains simultaneously, under the room temperature
60Co gamma-rays or high-power electron beam x ray irradiation x are crosslinked, can obtain difform gel through in difform mould, carrying out polymerization, and wherein solid content is 10～30%;
The described natural polymer of step (2) is selected one or more in glucosan, hyaluronic acid, chitosan, collagen, carrageenan, gelatin or the agar for use.
3. the method for preparing of a kind of hydrogel dressing with half interpenetrating network structure according to claim 1 and 2 is characterized in that, the molecular weight from 100 to 10000 of the hydroxyl carbowax described in the step (1).
4. the method for preparing of a kind of hydrogel dressing with half interpenetrating network structure according to claim 1 and 2 is characterized in that, the mass ratio of described acrylamide of step (2) and natural polymer is 0.1: 1～10: 1.
5. the method for preparing of a kind of hydrogel dressing with half interpenetrating network structure according to claim 1 is characterized in that, the redox initiation condition in the step (2) is that ultraviolet causes or thermal initiation, and wherein the condition of thermal initiation is 60～120 degrees centigrade.
6. the method for preparing of a kind of hydrogel dressing with half interpenetrating network structure according to claim 1 is characterized in that, the persulfate-N in the step (2), and N, N ', the concentration of N '-tetramethylethylenediamine redox system is 0.01～1wt%.
7. the method for preparing of a kind of hydrogel dressing with half interpenetrating network structure according to claim 2 is characterized in that, in the step (2)
60Co gamma-rays or high-power electron beam x ray irradiation x dosage are 10～80kGy.
8. a kind of hydrogel dressing with half interpenetrating network structure according to claim 1 or 2 said method preparations covers the application in the dressing at the temporary wound surface that promotes the wound surface skin healing.
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| CN101891946B (en) * | 2010-07-17 | 2012-07-04 | 厦门大学 | Enhanced biological hydrogel having DN-L structure and preparation method thereof |
| CN102690399B (en) * | 2012-06-14 | 2013-07-31 | 太原理工大学 | Polyaspartate/polyacrylic acid copolymer IPN (Interpenetrating Polymer Networks) hydrogel and preparation method thereof |
| CN103232611B (en) * | 2013-05-15 | 2014-12-24 | 南京斯瑞奇医疗用品有限公司 | Preparation method of novel medical hydrogel dressing |
| CN103230619B (en) * | 2013-05-15 | 2014-11-26 | 南京斯瑞奇医疗用品有限公司 | Composite hydrogel dressing and preparation method thereof |
| CN103980440A (en) * | 2014-04-28 | 2014-08-13 | 中科院广州化学有限公司南雄材料生产基地 | Semi-interpenetrating intelligent hydrogel and preparation method and application thereof |
| CN106562953B (en) * | 2016-11-07 | 2019-04-30 | 浙江大学 | Application, drug and process for preparing medicine of the hydroxyl radical carthamin yellow carthamus A in the drug of preparation treatment diabetic foot ulcer |
| CN108395509A (en) * | 2018-03-21 | 2018-08-14 | 广东电网有限责任公司电力科学研究院 | A kind of high molecular polymer and its preparation method and application with self-repair function |
| CN109580418A (en) * | 2019-01-20 | 2019-04-05 | 王忠良 | Harmful heavy metal detection method in a kind of cosmetics |
| CN110628047A (en) * | 2019-10-09 | 2019-12-31 | 安徽大学 | Preparation method of antibacterial agar acrylamide hydrogel |
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| CN1974608A (en) * | 2006-11-24 | 2007-06-06 | 清华大学 | Electronic beam radiopolymerization process of directly synthesizing temperature sensitive hydrogel |
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| CN1974608A (en) * | 2006-11-24 | 2007-06-06 | 清华大学 | Electronic beam radiopolymerization process of directly synthesizing temperature sensitive hydrogel |
Non-Patent Citations (1)
| Title |
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| 李斌等.聚乙二醇二丙烯酸酯齐聚物的合成及其红外激光固化性能研究.《高分子材料科学与工程》.2001,第17卷(第5期),第162-164页. * |
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