CN101161696B - Hydrogel and method for preparing same - Google Patents
Hydrogel and method for preparing same Download PDFInfo
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- CN101161696B CN101161696B CN2007101225799A CN200710122579A CN101161696B CN 101161696 B CN101161696 B CN 101161696B CN 2007101225799 A CN2007101225799 A CN 2007101225799A CN 200710122579 A CN200710122579 A CN 200710122579A CN 101161696 B CN101161696 B CN 101161696B
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Abstract
The present invention relates to a high strength hydrogel and a preparation method thereof. The method is firstly to perform a pre-irradiation and peroxidation process and then a thermal-initiated polymerization process. The pre-irradiation and peroxidation process is to irradiate the water soluble polymer or the water soluble polymer solution in the nitrogen atmosphere by the high energy radiation source to combine the peroxy group on the polymer chains; and the thermal-initiated polymerization process is to mix solution prepared by the water soluble polymer after initiated with the water soluble monomer or mix the water soluble polymer solution after initiated with the water soluble monomer, and then the product is obtained by deoxidizing and heating the mixture. The preparation method of hydrogel of the invention is simple, and the prepared hydrogel has a high mechanical strength, a wide selecting range of the raw materials, and a high applied cost.
Description
Technical field
The present invention relates to field of polymer technology.Hydrogel and preparation method thereof specifically utilizes the method for thermal-initiated polymerization after the first pre-irradiation peroxidation to prepare the method for high mechanical strength hydrogel.
Background technology
Owing in biomedicine and organizational engineering, have broad application prospects, nearly twenty or thirty over year progress in Intelligent Hydrogel become the focus of people's research gradually, wherein prepare the important directions that the hydrogel with high mechanical strength becomes people's research gradually, the meaning of preparation high mechanical strength hydrogel is that it has great potential using value as tissue timbering material, tissue substitute etc. in organizational engineering.
The physical strength of hydrogel is mainly by the order of hydrogel interior three-dimensional network structure and crosslinking degree decision, when the order of the three-dimensional network of hydrogel high more, crosslinking degree is high more, the physical strength of hydrogel is just high more, that is to say that the hydrogel with high mechanical strength generally will have regular three-dimensional net structure and higher cross-linking density.The method that tradition is improved hydrogel intensity mainly contains radiation method and chemical method, and wherein radiation method is that monomer solution is placed under the source of radiation, directly generates hydrogel through irradiation; Chemical method is that monomer, initiator, linking agent and solvent (mostly being water greatly) etc. are mixed, and makes monomer generation polymerization and crosslinked by heating, obtains hydrogel.But these two kinds of methods all are difficult to the length of macromolecular chain between control uniform distribution of cross-linking set and cross-linking set, thereby can not synthesize the hydrogel with homogeneous cross-linked network structure.And chemical method to prepare the process of hydrogel usually more complicated, preparation condition need change according to the select materials difference.United States Patent (USP) 2007/0179605A1 discloses a kind of high-intensity intercrossed network type hydrogel that has, its preparation process is: at first water-soluble polymer is dissolved in the buffered soln, and add light trigger and linking agent, under ultraviolet ray (UV) irradiation, cause radical polymerization and generate first network; Secondly the gel that forms in the mould is transferred in the water-soluble mono liquid solution that is added with light trigger and linking agent, causes radical polymerization again under UV irradiation, water-soluble monomer forms second cross-linked network between first network, and polymerization promptly gets product after finishing.In the disclosure technology, the preparation process complexity is loaded down with trivial details, mainly shows:
1) preparation process at first needs to carry out the process for preparation of buffered soln, the weighing process of linking agent and initiator, and these two processes all must accurately be prepared and weighing according to the aequum of water-soluble polymer and water-soluble monomer.Preferred UV irradiation causes radical polymerization in the disclosure patent, and carry out in the process at UV irradiation, at first need temperature is controlled, owing to can produce a large amount of heats during uviolizing, and too high temperature can cause negative impact to polymerization process, even can't obtain the product that will prepare, in order to keep carrying out under the disclosed room temperature in this patent the preparation condition of UV irradiation process, constantly temperature of reaction is regulated with regard to needs; In addition, the outer elicitation procedure of UV generally need carry out just reaching more than ten hours the purpose of preparation gel, and just needs UV continuous irradiation mixing solutions to guarantee that polymeric carries out in this process, because of this process need electric energy to keep the work of ultraviolet lamp.Disclose simultaneously in the disclosure patent and can adopt the mode of chemical method thermal initiation to prepare hydrogel, and this process still needs to carry out a large amount of loaded down with trivial details weighing linking agents and the process of initiator and preparation buffered soln.
2) must carry out continuously in the process of preparation first network and second network, up to obtaining finished product, make the preparation process longer duration, expend energy on is big.
3) in addition, adopt UV irradiation, in the irradiation process, produce a large amount of heats, generic container material adopting quartz glass, so the cost height of preparing product owing to adopt in the preparation hydrogel process.
4) owing to need to add initiator and linking agent in preparation process, and that these components more or less can exist in final product is residual, and it may bring potential harm to organism.
Summary of the invention
For this reason, technical problem to be solved by this invention is: a kind of simple method for preparing high intensity hydrogel at first is provided; Next provides a kind of high-intensity hydrogel that has by this method preparation.
For solving the problems of the technologies described above, a technical scheme of the present invention is:
A kind of method for preparing hydrogel, it may further comprise the steps: (1) pre-irradiation peroxidation process: in oxygen atmosphere, adopt high-energy radiation source irradiation water-soluble polymer; (2) thermal-initiated polymerization process: will mix with one or more water-soluble monomers that contain unsaturated carbon-to-carbon double bond and be mixed with solution through the described water-soluble polymer behind step (1) irradiation, again mixed solution is carried out deoxygenation, heating after, promptly get product.
Described water-soluble polymer in pre-irradiation peroxidation process is Powdered or water-soluble polymer solution; The described water-soluble monomer that one or more contain unsaturated carbon-to-carbon double bond in thermal-initiated polymerization process is a liquid or solid; Wherein said water-soluble polymer and described one or more contain unsaturated carbon-to-carbon double bond water-soluble monomer the two have one at least for solution.
Described water-soluble polymer is Polyvinylpyrolidone (PVP), polyene alcohols, polyacrylamide, polyacrylic, chitin kind, cellulose family, starch, protein or carbohydrate.
The described water-soluble monomer that contains unsaturated carbon-to-carbon double bond is vinylformic acid and derivative, acrylamide and derivative thereof, N-vinyl pyrrolidone, Hydroxyethyl acrylate, methoxy ethylene, Ba Dousuan, 2-acrylamide-2-methyl propane sulfonic acid, acrylic propanesulfonic acid, anhydrides, methacryloyl oxyethyl group aliquat, vinyl pyridine.
In the described pre-irradiation peroxidation process, temperature is 0-100 ℃ during irradiation, generally at room temperature gets final product, and irradiation dose is the 6-96 kilogray (kGy), and generally adopting irradiation dose is the high-energy radiation source of 100-400 gray(Gy) per minute, corresponding irradiation time 1-4 hour.Described high-energy radiation source is for producing the rumbatron of gamma-ray cobalt source or generation high-power electron beam.Source of radiation is divided into two kinds of low-energy radiation and high-energy radiations by energy region, and the low-energy radiation source mainly is UV-light and plasma body, the high-energy radiation source mainly be accelerator and
60The Co radioactive source.Wherein, lead to the situation of oxygen in the irradiation process, the then logical oxygen time is identical with irradiation time; And the situation of leading to oxygen at pre-irradiation, the then logical oxygen time is more than 1 hour.
In the described thermal-initiated polymerization process, Heating temperature is 30-70 ℃, and preferable reaction temperature is 35-45 ℃, and be more than 1 hour heat-up time.
Another technical scheme of the present invention is:
A kind of hydrogel with three-dimensional net structure is prepared by the method for claim 1-7, it is characterized in that: described three-dimensional net structure is by (1) water-soluble polymer chain; And (2) be made of the macromolecular chain that the polymerisation that contains unsaturated carbon-to-carbon double bond forms,
Wherein, the macromolecular chain that is polymerized is stated in the grafting of described water-soluble polymer chain to some extent, and has physical entanglement between the adjacent described macromolecular chain that is polymerized.
The described macromolecular chain that is polymerized comprises: I type chain promptly only has an end to graft on chain on the described water-soluble polymer chain; II type chain, promptly two ends all graft on the chain on the described water-soluble polymer chain; III type chain, promptly two ends all do not graft on one or more in the chain on the described water-soluble polymer chain.
Described water-soluble polymer is Polyvinylpyrolidone (PVP), polyene alcohols, polyacrylamide, polyacrylic, chitin kind, cellulose family, starch, protein or carbohydrate.
The described water-soluble monomer that contains unsaturated carbon-to-carbon double bond is vinylformic acid and derivative, acrylamide and derivative thereof, N-vinyl pyrrolidone, Hydroxyethyl acrylate, methoxy ethylene, Ba Dousuan, 2-acrylamide-2-methyl propane sulfonic acid, acrylic propanesulfonic acid, anhydrides, methacryloyl oxyethyl group aliquat, vinyl pyridine.
Described water-soluble polymer chain accounts for the 0.25-50% of hydrogel total mass; The described polymer that is polymerized accounts for the 5%-75% of hydrogel total mass; All the other components are water.
Through the hydrogel of the inventive method preparation, its intensity is significantly improved than the traditional water gel, generally can improve 1 to 2 order of magnitude.Reach more than 90% in water content and can bear higher stress, the highest pressure that bears nearly 30MPa.The sample of preparing covers light as far as possible to be preserved, and wraps up and prevent dehydration.After the several months placement, character does not almost change.
Technique scheme of the present invention has tangible advantage compared to existing technology, and promptly method is simple, and is easy and simple to handle, is mainly reflected in:
1) adopt the method for pre-irradiation to prepare the preparation process that hydrogel has been simplified hydrogel greatly, only need water-soluble polymer solution is handled through pre-irradiation, mode through deoxygenation, thermal initiation can be reacted with monomer, and do not need to add any initiator and linking agent, chemical initiated polymerization method has compared to prior art been simplified the complicated loaded down with trivial details experimental implementation such as process for preparation, the preparation feedback process of solution greatly.
2) pre-irradiation peroxidation process and thermal-initiated polymerization process can be carried out respectively, do not disturb mutually.Because water-soluble polymer or water-soluble polymer solution behind the pre-irradiation can be deposited the long period, thereby described water-soluble polymer or water-soluble polymer solution need not carry out pre-irradiation peroxidation process immediately after pre-irradiation peroxidation process, that is to say that pre-irradiation peroxidation process and thermal-initiated polymerization process needn't carry out continuously in strictness, therefore can measure according to demand in advance big content of starting materials is carried out irradiation, can not be subjected to pining down of next step thermal-initiated polymerization process.
3) the product preparation process does not all have special requirement to equipment and the container of selecting for use, so the cost of preparing product is not high.
4) hydrogel by the present invention preparation has high strength, and polymer and this three part of water of only being formed by water-soluble polymer, polymerisation form, and does not have the residual of other compositions, and the potential threat when being applied to organism is reduced to minimum.In addition, because it has the favorable mechanical performance, so other Application Areass that can also be used for the hydrogel physical strength is had higher requirements.
Description of drawings
For the easier quilt of content of the present invention is clearly understood, below according to a particular embodiment of the invention and in conjunction with the accompanying drawings, the present invention is further detailed explanation.At first accompanying drawing is carried out brief description, wherein:
Fig. 1 is the functional block diagram of preparation hydrogel in the one embodiment of the invention;
Fig. 2 utilizes iodimetry,iodometry to measure peroxide level with change curve storage period in the one embodiment of the invention, wherein X-coordinate is storage period, and unit is the sky, and ordinate zou is a peroxide level, and unit is every milliliter of a mole.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, but should be noted that these embodiment only are used to method of the present invention is described, and scope of the present invention can not be confined to this.
As shown in the functional block diagram of preparation hydrogel in Fig. 1 one embodiment of the invention, the preparation process of hydrogel can be divided into pre-irradiation peroxidation process and thermal-initiated polymerization process, respectively these two processes is described below.
Pre-irradiation peroxidation process
In oxygen atmosphere, water-soluble polymer is placed irradiation for some time under the energetic ray, purpose is to produce a large amount of peroxy-radicals on described water-soluble polymer chain, wherein, water-soluble polymer is Powdered or is water-soluble polymer solution.The approach that realizes oxygen atmosphere comprises: 1) at pre-irradiation aerating oxygen in water-soluble polymer powder or water-soluble polymer solution, the time of aerating oxygen is preferred more than 1 hour; 2) in the irradiation process in the water-soluble polymer powder or the water-soluble polymer aqueous solution aerating oxygen, the time of aerating oxygen is identical with irradiation time.Wherein, the major cause of water-soluble polymer state preferred powder powder or water-soluble polymer solution is, in logical oxygen process, oxygen contacts as much as possible with the water-soluble polymer chain, make to produce a large amount of peroxy-radicals on the water-soluble polymer chain, provide safeguard for generating described hydrogel three-dimensional network structure in next step.
By iodimetry,iodometry test proof, the peroxy-radical on the water-soluble polymer chain after the pre-irradiation peroxidation can keep active for a long time and not decompose under the protection of oxygen.As shown in Figure 2, in one embodiment, the water-soluble polymer low temperature after the pre-irradiation peroxidation was placed after 1 month, and the peroxy-radical content in the water-soluble polymer still can reach every milliliter more than 4 moles.Through contrast experiment repeatedly, under the constant situation of other preparation conditions, select for use the physical strength of the hydrogel that the water-soluble polymer of placing the different time points in month prepares not have significant difference.
Can find out by last analysis, the pre-irradiation peroxidation method that the present invention adopts not only can be saved weighing process loaded down with trivial details in the chemical method, and owing to the water-soluble polymer after the pre-irradiation peroxidation can be deposited the long period, such as one month, and ready access upon use as required, thereby water-soluble polymer need not carry out thermal-initiated polymerization process immediately after pre-irradiation peroxidation process, that is to say that pre-irradiation peroxidation process and thermal-initiated polymerization process needn't carry out continuously in strictness, therefore can measure according to demand in advance big content of starting materials is carried out irradiation, and can not be subjected to pining down of next step thermal-initiated polymerization process, simplified the preparation process of hydrogel to a great extent.
Thermal-initiated polymerization process
The water-soluble monomer that water-soluble polymer after the pre-irradiation peroxidation and one or more are contained unsaturated carbon-to-carbon double bond mixes and is mixed with solution, remove the oxygen in the system again, the mixing solutions that will mix and remove oxygen heats then, promptly get product after for some time, wherein, water-soluble monomer is a liquid or solid, and water-soluble polymer and described one or more contain unsaturated carbon-to-carbon double bond water-soluble monomer the two have one at least for solution.Described thermal-initiated polymerization process can be divided into oxygen removal process and heat-processed again, respectively oxygen removal process and heat-processed is further specified below.
Oxygen removal process: in system, feed the nitrogen or the rare gas element of certain hour, oxygen is discharged.Deoxygenation former because: because oxygen has restraining effect to the activity of the peroxy radical that obtained by the peroxy-radical decomposition, that is to say, in order to make the peroxy-radical on the macromolecular chain be decomposed into peroxy radical, just need remove the oxygen in the mixing solutions with trigger monomer polymerization activity.Wherein, the deoxygenation time was generally 1-30 minute; The deoxygenation temperature is controlled at generally that room temperature is following to get final product, and preferably carries out at low temperatures, in one embodiment, the container that holds mixing solutions is positioned over carries out oxygen removal process in the frozen water mixed solution.The major cause of carrying out deoxygenation under the preferred low temperature is, carrying out along with oxygen removal process, oxygen content reduces gradually in the mixing solutions, the activity of the peroxy radical that is decomposed to form on a small quantity in the system increases thereupon, local monomer can occur and be initiated the polymeric situation, and owing to do not reach kick off temperature this moment, so the monomer-polymer molecular chain that generates is shorter, be unfavorable for forming regular network structure, therefore monomer is initiated this situation of polymeric in oxygen removal process in order to reduce, and the temperature during deoxygenation is controlled under the low temperature of trying one's best.
Heat-processed: will remove behind the oxygen mixing solutions at a certain temperature reacting by heating promptly get product after for some time.The formation mechanism of hydrogel is: as shown in Figure 1, the peroxy-radical decomposes that is evenly distributed on the macromolecular chain becomes peroxy radical, cause the water-soluble polymer chain water-soluble monomer generation Raolical polymerizable that contains unsaturated carbon-to-carbon double bond on every side, prolongation along with the reaction times, the macromolecular chain that grafts on the described water-soluble monomer generation on the water-soluble polymer chain uniformly constantly increases, and along with the growth of these macromolecular chains, interchain entanglement degree constantly increases, and finally forms regular three-dimensional net structure.
As shown in fig. 1, in the final hydrogel three-dimensional network that forms, mainly there are three kinds of forms in the macromolecular chain that water-soluble monomer generates, is respectively:
(1) I type chain: promptly only have an end to graft on macromolecular chain on the water-soluble polymer chain.The forming process of I type chain is: after water-soluble monomer was caused by the free radical on the water-soluble polymer chain, molecular chain constantly increased, and the small molecules free radical generation chain termination reaction in the last and system finally forms I type chain.Between the I type chain between the adjacent water-soluble polymer chain physical entanglement taking place, forms physical crosslinking.The physical crosslinking point that forms is along with the prolongation in reaction times increases gradually, and the physical strength of hydrogel increases thereupon.The characteristics of I type chain are that mode with chemically crosslinked is connected with water-soluble polymer for an end is only arranged, and in the swelling behavior process, water molecules can destroy the physical crosslinking in the three-dimensional network and can not destroy chemically crosslinked.
(2) II type chain: promptly two ends all graft on the macromolecular chain on the described water-soluble polymer chain.The forming process of II type chain is: after water-soluble monomer is caused by the free radical on the water-soluble polymer chain, molecular chain constantly increases, grafted finally forms II type chain by the macromolecular chain generation double-basis stopped reaction that polymerisation forms on the last and adjacent water-soluble polymer chain.This chain two ends all are grafted on the water-soluble polymer chain with the form of chemically crosslinked, can not destroyed by water molecules in the swelling behavior process, therefore play the fixedly effect of hydrogel network skeleton, guarantee that gel can not be dissolved in the water;
(3) III type chain: promptly two ends all do not graft on the macromolecular chain on the described water-soluble polymer chain.The forming process of III type chain is: owing to have free small molecules peroxy-radical in the water-soluble polymer solution after the irradiated oxidation, form free small molecules peroxy radical in the heat-processed, water-soluble monomer is by these free small molecules peroxy radical initiated polymerizations, and last and small molecules peroxy radical generation chain termination reaction, finally form III type chain.These III type chains intert or are wound in the hydrogel three-dimensional network, play as the time spent and strengthen the meet with stresses effect of ability of chain bundle in the network being subjected to external stress.
In sum, in pre-irradiation peroxidation process, because peroxy radical is evenly distributed on the water-soluble polymer chain, guaranteed after thermal-initiated polymerization process in, what the macromolecular chain that polymerisation forms can be evenly distributed is grafted on these water-soluble polymer chains, and, realized the regularity and the high crosslink density of the structure of hydrogel by the regular relatively orderly three-dimensional net structure of the final formation of physical entanglement closely.Because peroxy-radical density is bigger on the water-soluble polymer chain, cause the grafted chain ratio that produces by peroxy radical and be easier to mutual entanglement and form chain bundle, and chain bundle is interior, all there is strong hydrogen bond force effect in interchain.When gel was in confined state, original water-soluble polymer chain and three kinds of graft polymer chains were simultaneously stressed, and stress can disperse rapidly; When gel is in when being stretched state, all polymer long-chains are all had very big flexible scope, dispersive stress so to a great extent from free state to stretching to open fully.Through measuring, the hydrogel that adopts the present invention's preparation is when water content 90%, and the compressive strength that hydrogel can bear can reach one substantially, and maximum can reach tens of MPas more than the MPa, meets or exceeds the compressive strength that the human muscle can bear.The preparation process of whole hydrogel is all carried out under normal pressure, and the easy and condition of method is controlled easily.
More than the preparation principle of hydrogel is described and describes, below in conjunction with embodiment the method and apparatus that the present invention prepares hydrogel is further described and describes, provide in addition that embodiment compares among Comparative Examples and the present invention, can know the advantage of understanding the embodiment of the invention more.But should be noted that these embodiment only are used to method and apparatus of the present invention is described, and scope of the present invention can not be confined to this.
Embodiment 1
In polyvinylpyrrolidone PVP (K30) powder, led to oxygen 1 hour before the pre-irradiation, adopted brill source irradiation 4 hours, temperature is 100 ℃ during irradiation, dose rate is 200 gray(Gy) per minutes, after pre-irradiation finishes, PVP powder and water are mixed with solution, solution is mixed with vinylformic acid, and the quality percentage composition of PVP is 0.25% in the mixed solution, and acrylic acid quality percentage composition is 74.75%, logical nitrogen will hold mixing solutions after 15 minutes container sealing is heated, temperature of reaction is 70 ℃, reacts promptly to get product after 12 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 10mm/min.Measure, this sample moisture content is 80%, and its compressive strength is 1.45MPa.
Embodiment 2
Is that 1/3 ratio and water are mixed with solution with polyvinyl alcohol (the dealcoholysis degree is more than 90%) in mass ratio, adopted the logical oxygen irradiation in cobalt source 1 hour, temperature is 40 ℃ during irradiation, radiation dose rate 300 gray(Gy) per minutes, after irradiation finishes, solution is mixed with acrylamide, the quality percentage composition of polyvinyl alcohol is 15% in the mixed solution, and the quality percentage composition of acrylamide is 40%, and logical argon gas is after 30 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 35 ℃, reacts promptly to get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 24.36MPa.
Embodiment 3
Is that 1/20 ratio and water are mixed with solution with cm-chitosan in mass ratio, adopted the logical oxygen irradiation in cobalt source 3 hours, temperature is 0 ℃ during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with the N-vinyl pyrrolidone, the quality percentage composition of cm-chitosan is 2.4% in the mixed solution, and the quality percentage composition of N-vinyl pyrrolidone is 49.6%, and helium injection gas is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 50 ℃, reacts promptly to get product after 3 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 80%, compressive strength is 9.41MPa.
Embodiment 4
Is that 1/30 ratio and water are mixed with solution with PVP (K30) in mass ratio, adopted the logical oxygen irradiation in cobalt source 2.5 hours, temperature is 35 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, and the quality percentage composition of PVP is 1.25% in the mixed solution, and acrylic acid quality percentage composition is 61.25%, logical nitrogen is after 1 minute, the container sealing that holds mixing solutions is heated, and temperature of reaction is 45 ℃, reacts promptly to get product after 8 hours, during product water content 90%, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 90%, compressive strength is 10.60MPa, and during water content 80%, compressive strength is 21.09MPa.
Comparative Examples 1
Provide Comparative Examples 1 at embodiment 4, this Comparative Examples adopts traditional irradiation method to prepare hydrogel.Is that 1/30 ratio and water are mixed with solution with PVP (K30) in mass ratio, solution is mixed with vinylformic acid, the quality percentage composition of PVP is 1.25% in the mixed solution, acrylic acid quality percentage composition is 61.25%, logical nitrogen is after 1 minute, the container sealing of mixing solutions will be held, adopted cobalt-60 radiosterilize 2.5 hours, temperature is 35 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, irradiation promptly gets product after finishing, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 90%, compressive strength is 0.1MPa.
Comparative Examples 2
Provide Comparative Examples 2 at embodiment 4, this Comparative Examples adopts traditional chemical method to prepare hydrogel.Is that 1/30 ratio and water are mixed with solution with PVP (K30) in mass ratio, solution is mixed with vinylformic acid, the quality percentage composition of PVP is 1.25% in the mixed solution, acrylic acid quality percentage composition is 61.25%, add initiator ammonium persulfate, the quality percentage composition is 0.5% of a solution solid content, and add the linking agent methene, and the quality percentage composition is 0.5% of a solution solid content, logical nitrogen is after 1 minute, the container sealing that holds mixing solutions is heated, temperature of reaction is 45 ℃, reacts promptly to get product after 8 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 90%, compressive strength is 0.05MPa, and during water content 80%, compressive strength is 0.31MPa.
Comparative Examples is analyzed
By Comparative Examples 1,2, as can be seen, the physical strength of the hydrogel that the employing radiation method is prepared is low, and adopt chemical method to prepare the process complexity of hydrogel, need go out the amount of initiator and linking agent and carry out accurate weighing according to water-soluble polymer and water-soluble monomer cubage, the compressive strength that hydrogel had that employing radiation method and chemical method are prepared be all far below the compressive strength that adopts the hydrogel for preparing among the present invention.
Embodiment 5
In polyacrylamide (C-PAM) powder, led to oxygen 4 hours before the pre-irradiation, adopted the logical oxygen irradiation in cobalt source 1 hour, temperature is 80 ℃ during irradiation, dose rate is 200 gray(Gy) per minutes, after pre-irradiation finishes, the C-PAM powder is mixed with Ba Dousuan solution, the quality percentage composition of C-PAM is 5% in the mixed solution, the quality percentage composition of Ba Dousuan is 45%, and logical nitrogen will hold mixing solutions after 5 minutes container sealing is heated, and temperature of reaction is 50 ℃, react and promptly get product after 10 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 15mm/min.Measure, during this sample moisture content 85%, compressive strength is 6.32MPa.
Embodiment 6
Is that 1/1 ratio and water are mixed with solution with polyacrylic acid in mass ratio, logical oxygen is after 2 hours, adopted cobalt-60 radiosterilize 2 hours, temperature is 60 ℃ during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with monomer mixed solution, polyacrylic quality percentage composition is 40%, and the quality percentage composition of mixed monomer solution is 20%, and all the other components are water, wherein said monomer mixed solution is 2-acrylamide-2-methyl propane sulfonic acid (AMPS) and the acrylic propanesulfonic acid is that 10: 1 mixed forms by mass ratio, logical nitrogen after 1 minute heats the container sealing that holds mixing solutions, and temperature of reaction is 30 ℃, react and promptly get product after 48 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 90%, compressive strength is 9.64MPa.
Embodiment 7
Adopting the hot-water process is that 1/6 ratio and water are mixed with solution with methylcellulose gum in mass ratio, adopted the logical oxygen irradiation in cobalt source 3 hours, temperature is 20 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, after irradiation finishes, solution is mixed with monomer mixed solution, the quality percentage composition of methylcellulose gum is 7% in the mixed solution, the quality percentage composition of monomer mixed solution is 51%, wherein said monomer mixed solution is hydroxy ethyl methacrylate and methoxy ethylene by mass ratio is that 4: 1 mixed forms, logical nitrogen after 5 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 40 ℃, react and promptly get product after 6 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 80%, compressive strength is 26.65MPa.
Embodiment 8
Is that 1/6 ratio and water are mixed with solution with water soluble starch in mass ratio, logical oxygen is after 4 hours, adopted cobalt-60 radiosterilize 2 hours, temperature is 50 ℃ of radiation dose rates, 200 gray(Gy) per minutes during irradiation, after irradiation finishes, solution is mixed with monomer mixed solution, the quality percentage composition of water soluble starch is 10% in the mixed solution, the quality percentage composition of monomer mixed solution is 30%, wherein said monomer mixed solution is vinyl pyridine and Pyroglutaric acid by mass ratio is that 6: 1 mixed forms, logical nitrogen after 5 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 44 ℃, react and promptly get product after 12 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 85%, compressive strength is 17.93MPa.
Embodiment 9
In water-soluble collagen protein powder, led to oxygen 3 hours before the pre-irradiation, adopted the logical oxygen irradiation in cobalt source 4 hours, temperature is 70 ℃ during irradiation, dose rate is 200 gray(Gy) per minutes, pre-irradiation finishes the water-soluble collagen albumen in back and water is mixed with solution, described solution is mixed with methacrylic acid, the proteic quality percentage composition of water-soluble collagen is 14.5% in the mixed solution, the quality percentage composition of methacrylic acid is 42%, logical nitrogen is after 5 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 41 ℃, reacts promptly to get product after 12 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 21.04MPa.
Embodiment 10
Is that 1/9 ratio and water are mixed with solution with PVP (K30) in mass ratio, adopted the logical oxygen irradiation in cobalt source 1.5 hours, temperature is 25 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, after irradiation finishes, solution is mixed with AMPS, the quality percentage composition of PVP is 2.5% in the mixed solution, and the quality percentage composition of AMPS is 75%, and logical nitrogen is after 5 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 37 ℃, reacts promptly to get product after 12 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 19.04MPa.
Embodiment 11
Is that 1/2 ratio and water are mixed with solution with poly N-isopropyl acrylamide in mass ratio, adopted the logical oxygen irradiation in cobalt source 4 hours, temperature is 10 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of poly N-isopropyl acrylamide is 21.5% in the mixed solution, and acrylic acid quality percentage composition is 35.5%, and logical argon gas is after 3 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 43 ℃, reacts promptly to get product after 1 hour, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 85%, compressive strength is 25.61MPa.
Embodiment 12
In the polyoxyethylene glycol powder, led to oxygen 3 hours before the pre-irradiation, adopted cobalt-60 radiosterilize 4 hours, temperature is 15 ℃ during irradiation, dose rate is 300 gray(Gy) per minutes, pre-irradiation finishes the back polyoxyethylene glycol and water is mixed with solution, described solution is mixed with AMPS, the quality percentage composition of polyoxyethylene glycol is 10% in the mixed solution, and the quality percentage composition of AMPS is 30%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 42 ℃, reacts promptly to get product after 6 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 80%, compressive strength is 20.04MPa.
Embodiment 13
Is that 1/60 ratio and water are mixed with solution with polymethyl acrylic acid in mass ratio, logical oxygen is after 2 hours, adopted cobalt-60 radiosterilize 3 hours, temperature is a room temperature during irradiation, radiation dose rate 400 gray(Gy) per minutes, irradiation mixes solution after finishing with vinylformic acid, the quality percentage composition of polymethyl acrylic acid is 0.5% in the mixed solution, acrylic acid quality percentage composition is 69.5%, logical nitrogen after 10 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 36 ℃, react and promptly get product after 36 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 18.55MPa.
Embodiment 14
Is that 1/100 ratio and water are mixed with solution with polyoxyethylene in mass ratio, logical oxygen is after 3 hours, adopted cobalt-60 radiosterilize 3 hours, temperature is 60 ℃ during irradiation, radiation dose rate 350 gray(Gy) per minutes, irradiation mixes solution after finishing with vinylformic acid, the quality percentage composition of polyoxyethylene is 0.5% in the mixed solution, the quality percentage composition of mixed monomer solution is 49.5%, logical nitrogen after 10 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 44 ℃, react and promptly get product after 48 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 19.06MPa.
Embodiment 15
Is that 1/29 ratio and water are mixed with solution with polymaleic acid in mass ratio, logical oxygen is after 2 hours, adopted cobalt-60 radiosterilize 2 hours, temperature is 50 ℃ during irradiation, radiation dose rate 250 gray(Gy) per minutes, irradiation mixes solution after finishing with vinylformic acid, the quality percentage composition of polymaleic acid is 1.5% in the mixed solution, the quality percentage composition of mixed monomer solution is 55%, logical nitrogen after 10 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 38 ℃, react and promptly get product after 36 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 10mm/min.Measure, during this sample moisture content 90%, compressive strength is 18.13MPa.
Embodiment 16
Adopting the hot-water process is that 1/10 ratio and water are mixed with solution with the sulfonic acid ethyl cellulose in mass ratio, adopted the logical oxygen irradiation in cobalt source 3 hours, temperature is 20 ℃ during irradiation, radiation dose rate 300 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of sulfonic acid ethyl cellulose is 6% in the mixed solution, and acrylic acid quality percentage composition is 34%, and logical nitrogen is after 15 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 70 ℃, reacts promptly to get product after 2 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 20mm/min.Measure, during this sample moisture content 90%, compressive strength is 2.63MPa.
Embodiment 17
Adopting the hot-water process is that 1/5 ratio and water are mixed with solution with carboxymethyl hydroxyethyl cellulose in mass ratio, adopted the logical oxygen irradiation in brill source 3 hours, temperature is 20 ℃ during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of carboxymethyl hydroxyethyl cellulose is 9% in the mixed solution, and acrylic acid quality percentage composition is 46%, and logical nitrogen is after 15 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 33 ℃, reacts promptly to get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 19.47MPa.
Embodiment 18
Adopting the hot-water process is that 1/11 ratio and water are mixed with solution with methylcellulose gum in mass ratio, adopted the logical oxygen irradiation in cobalt source 2 hours, temperature is 40 ℃ during irradiation, radiation dose rate 200 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of methylcellulose gum is 3.5% in the mixed solution, and acrylic acid quality percentage composition is 58%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 48 ℃, reacts promptly to get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 15mm/min.Measure, during this sample moisture content 90%, compressive strength is 8.64MPa.
Embodiment 19
Adopting the hot-water process is that 1/39 ratio and water are mixed with solution with hydroxyethylmethyl-cellulose in mass ratio, adopted the logical oxygen irradiation in cobalt source 2 hours, temperature is a room temperature during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with methacrylic acid, the quality percentage composition of hydroxyethylmethyl-cellulose is 1.25% in the mixed solution, and the quality percentage composition of methacrylic acid is 50%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 43 ℃, reacts promptly to get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 25.04MPa.
Embodiment 20
Adopting the hot-water process is that 1/20 ratio and water are mixed with solution with water soluble polyurethane resin in mass ratio, adopted the logical oxygen irradiation in cobalt source 2 hours, temperature is a room temperature during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of water soluble polyurethane resin is 2.75% in the mixed solution, and acrylic acid quality percentage composition is 42.25%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 51 ℃, reacts promptly to get product after 1 hour, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 15mm/min.Measure, during this sample moisture content 90%, compressive strength is 4.81MPa.
Embodiment 21
Is that 1/29 ratio and water are mixed with solution with xanthan gum in mass ratio, adopted the logical oxygen irradiation in brill source 1 hour, temperature is a room temperature during irradiation, radiation dose rate 100 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of xanthan gum is 2% in the mixed solution, and acrylic acid quality percentage composition is 40%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 42 ℃, reacts promptly to get product after 48 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 90%, compressive strength is 22.16MPa.
Embodiment 22
Adopting the hot-water process is that 1/7 ratio and water are mixed with solution with carboxymethyl starch in mass ratio, adopted the logical oxygen irradiation in cobalt source 4 hours, temperature is a room temperature during irradiation, radiation dose rate 400 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of water soluble polyurethane resin is 5% in the mixed solution, and acrylic acid quality percentage composition is 60%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 47 ℃, reacts promptly to get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 20mm/min.Measure, during this sample moisture content 90%, compressive strength is 3.34MPa.
Embodiment 23
Is that 1/4 ratio and water are mixed with solution with water soluble starch in mass ratio, logical oxygen is after 4 hours, adopted brill source irradiation 2 hours, temperature is 50 ℃ of radiation dose rates, 200 gray(Gy) per minutes during irradiation, after irradiation finishes, solution is mixed with monomer mixed solution, the quality percentage composition of water soluble starch is 50% in the mixed solution, the quality percentage composition of monomer mixed solution is 5%, wherein said monomer mixed solution is vinyl pyridine and Pyroglutaric acid by mass ratio is that 5: 1 mixed forms, logical nitrogen after 5 minutes heats the container sealing that holds mixing solutions, and temperature of reaction is 40 ℃, react and promptly get product after 24 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength to be tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 85%, compressive strength is 2.91MPa.
Embodiment 24
Is that 1/10 ratio and water are mixed with solution with the polyoxyethylene glycol powder in mass ratio, adopted brill source irradiation 2.5 hours, temperature is 35 ℃ during irradiation, dose rate is 300 gray(Gy) per minutes, after pre-irradiation finishes, polyglycol solution is mixed with AMPS, the quality percentage composition of polyoxyethylene glycol is 45% in the mixed solution, and the quality percentage composition of AMPS is 11%, and logical nitrogen is after 15 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 45 ℃, reacts promptly to get product after 12 hours, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 85%, compressive strength is 6.64MPa.
Embodiment 25
Adopting the hot-water process is that 1/20 ratio and water are mixed with solution with water soluble polyurethane resin in mass ratio, adopted the logical oxygen irradiation in cobalt source 2 hours, temperature is a room temperature during irradiation, radiation dose rate 350 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of water soluble polyurethane resin is 42.5% in the mixed solution, and acrylic acid quality percentage composition is 15%, and logical nitrogen is after 10 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 51 ℃, reacts promptly to get product after 1 hour, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 15mm/min.Measure, during this sample moisture content 90%, compressive strength is 4.16MPa.
Embodiment 26
Is that 1/10 ratio and water are mixed with solution with poly N-isopropyl acrylamide in mass ratio, adopted electron accelerator irradiation 4 hours, temperature is 20 ℃ during irradiation, radiation dose rate 250 gray(Gy) per minutes, after irradiation finishes, solution is mixed with vinylformic acid, the quality percentage composition of poly N-isopropyl acrylamide is 39% in the mixed solution, and acrylic acid quality percentage composition is 26%, and logical argon gas is after 3 minutes, the container sealing that holds mixing solutions is heated, temperature of reaction is 43 ℃, reacts promptly to get product after 1 hour, under 25 ℃ of conditions, with the electronics universal testing machine its compressive strength is tested, control crossbeam speed is 5mm/min.Measure, during this sample moisture content 80%, compressive strength is 15.61MPa.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of the invention.
Claims (5)
1. method for preparing hydrogel, it may further comprise the steps:
(1) pre-irradiation peroxidation process: in oxygen atmosphere, adopt high-energy radiation source irradiation water-soluble polymer, temperature is 0-100 ℃ during irradiation, irradiation dose is the 6-96 kilogray (kGy), described water-soluble polymer is a Polyvinylpyrolidone (PVP), polyacrylamide, poly N-isopropyl acrylamide, polyacrylic acid, polymethyl acrylic acid, cm-chitosan, methylcellulose gum, the sulfonic acid ethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethylmethyl-cellulose, water soluble starch, water-soluble collagen albumen, polyoxyethylene glycol, polyoxyethylene, polymaleic acid, water soluble polyurethane resin or xanthan gum;
(2) thermal-initiated polymerization process: will mix with one or more water-soluble monomers that contain unsaturated carbon-to-carbon double bond and be mixed with solution through the described water-soluble polymer behind step (1) irradiation, after again mixed solution being carried out deoxygenation, heating, promptly get product, in the described mixed solution, described water-soluble polymer accounts for the 0.25-50% of total mass; The described water-soluble monomer that contains unsaturated carbon-to-carbon double bond accounts for the 5%-75% of total mass; All the other components are water; Heating temperature is 30-70 ℃, be more than 1 hour heat-up time, wherein, the described water-soluble monomer that contains unsaturated carbon-to-carbon double bond is vinylformic acid, methacrylic acid, hydroxy ethyl methacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic acid, N-vinyl pyrrolidone, Ba Dousuan or vinyl pyridine.
2. the method for preparing hydrogel as claimed in claim 1 is characterized in that: described high-energy radiation source is for producing the rumbatron of gamma-ray cobalt source or generation high-power electron beam.
3. the method for preparing hydrogel as claimed in claim 1 or 2 is characterized in that: in the described thermal-initiated polymerization process: carry out deoxygenation by feeding nitrogen and/or rare gas element in described mixed solution.
4. the hydrogel with three-dimensional net structure is prepared by any described method of claim 1-3, it is characterized in that: described three-dimensional net structure by:
(1) water-soluble polymer chain; And
(2) macromolecular chain that is formed by the polymerisation that contains unsaturated carbon-to-carbon double bond constitutes,
Wherein, the macromolecular chain that is polymerized is stated in the grafting of described water-soluble polymer chain to some extent, and has physical entanglement between the adjacent described macromolecular chain that is polymerized; Described water-soluble polymer chain accounts for the 0.25-50% of hydrogel total mass; The described polymer that is polymerized accounts for the 5%-75% of hydrogel total mass; All the other components are water.
5. hydrogel as claimed in claim 4 is characterized in that: the described macromolecular chain that is polymerized comprise following one or more:
I type chain promptly only has an end to graft on chain on the described water-soluble polymer chain;
II type chain, promptly two ends all graft on the chain on the described water-soluble polymer chain;
III type chain, promptly two ends all do not graft on the chain on the described water-soluble polymer chain.
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| CN102351992A (en) * | 2011-07-11 | 2012-02-15 | 武汉纺织大学 | Preparation method of flocculation starch of grafting acrylamide |
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