A kind of preparation method of highly-breathable medical gel materialTechnical field
The present invention relates to a kind of preparation methods of highly-breathable medical gel material, belong to medical material tech field.
Background technique
Gel rubber material, also known as cementitious matter.Under physics, chemical action, firm Shi Zhuanti can be become from slurry, and can glueUnclassified stores is tied, the substance of the complex solid of certain mechanical strength is formed with.It is all to pass through a series of objects in civil engineering materialShot shape or bulk material can be bonded integral material by reason, chemical change, be referred to as gel rubber material.Gel rubber material refers to logicalThe physics chemical action for crossing itself can glue shot or bulk material during becoming hard stone shape body from plasticity slurryForm for whole material, also known as cementing material.
It is poly- that macromolecule hydrogel may be defined as the crosslinking that can be swollen in water and keep large quantity of moisture and cannot be dissolvedClose object.According to the difference of cross-linked network bonding mechanism, hydrogel can be divided into physical gel and chemical gel, and physical gel is to pass throughThe gel that the modes such as the physical action such as entanglement of electrostatic interaction, hydrogen bond, chain are formed, this gel be it is non-permanent, by addingHeat, gel can be changed into colloidal sol, so also referred to as heat-convertible gel.Chemical gel is having of being cross-linked to form by chemical bondThe polymer of three-dimensional net structure is permanent, also known as true gel.Injectable gel is the novel water-setting occurred in recent yearsGel Precursor with certain fluidity is implanted in vivo by glue by way of injection, and gel, which can be full of, entirely to be hadThe defect of irregular character, operation wound are small.Injection aquagel acts not only as tissue renovation material, can also makeFor surface of a wound sealing agent, it is closed the surface of a wound, prevents leakage, gas leakage.
The main indicator for evaluating dressing performance is as follows: mechanical performance；Bacterial barriers effect: ideal Wound dressing should be able to be rightMicroorganism invasion plays the role of barrier.Adhesiveness: i.e. dressing is uniform, is closely adhere to the ability of the surface of a wound.Absorptive capacity: i.e.Dressing absorbs the ability of wound fluid and harmful substance.Moisture-vapor transmission: moisture-vapor transmission appropriate can be such that the surface of a wound protectsAn ideal humidity environment is held, it is wet to prevent from being also able to maintain the surface of a wound while hydrops, may advantageously facilitate healing.Oxygen is penetratingProperty: oxygen can be improved fibroblastic activity.
Wherein gas permeability and expansion rate of water absorption and disinfection effect have higher influence, related patent hair to gel rubber materialBright medical gel material forms the powder solid content of supermolecule by polysaccharide and crosslinking action, and it is swollen to have very good water suctionSwollen rate.But the medical gel permeability of its preparation is undesirable and disinfection effect is bad.Therefore, it invents a kind of highGas medical gel material has positive effect to medical material tech field.
Summary of the invention
The technical problems to be solved by the invention: bad for current medical gel material disinfection effect, saturating simultaneouslyThe defect of gas effect difference, provides a kind of preparation method of highly-breathable medical gel material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of preparation method of highly-breathable medical gel material, it is characterised in that specific preparation step are as follows:
(1) it weighs the chopping of 300~400g Chinese aloe leaf to be placed in a beaker, is poured into sodium hydroxide solution and impregnate Chinese aloe leaf in beaker,It places the beaker constant temperature in water-bath to impregnate, be cooled to room temperature after immersion, it is mixed to the obtained solid-liquid of neutrality that salt acid for adjusting pH value is added dropwiseClose object；
(2) cellulase of solidliquid mixture quality 2~4% is added into above-mentioned beaker, places the beaker in sonic oscillation instrument,Filtrate is obtained by filtration after oscillation, it is spare；
(3) according to parts by weight, 1.4~1.7 parts of ferric trichlorides, 4.8~5.2 parts of sodium acetates, 0.4~0.6 part of citric acid are weighedIt is uniformly mixed obtained mixed liquor in sodium and 80~90 parts of ethylene glycol investment reaction kettles, reaction kettle is heated up and carries out isothermal reaction, insteadShould after filter residue is obtained by filtration, be put into after being washed with distilled water 3~5 times in vacuum oven and dry reaction solid product be made；
(4) according to parts by weight, 3~5 parts of above-mentioned reaction solid products, 50~55 parts of spare filtrates, 1.0~1.2 parts are weighedIn urea and 14~18 parts of distilled water investment three-necked flasks, mixed emulsion is mixed with blender, three-necked flask is placed in micro-It is heated in wave furnace, is put into vacuum oven and is concentrated and dried until product constant weight, is made reacting slurry after heating；
(5) according to parts by weight, 2~3 parts of chitosans, 6~7 parts of potassium hydroxide powders, 20~22 parts of urea powders and 60 are weighedIt is stirred evenly in~65 parts of distilled water investment beakers, places the beaker and stand obtained reactant in household freezer, according to parts by weight,It will be stirred in 13~14 parts of above-mentioned reacting slurries, 20~22 parts of reactants and 1.5~1.8 parts of sodium carboxymethylcellulose investment beakersIt mixes, mixed glue solution is made；
(6) above-mentioned mixed glue solution is placed in reaction kettle, increases reactor temperature reaction, be added after reaction into reaction kettle mixed2.0~2.5 times of glue quality of distilled water is closed, reaction is made prefabricated glue, prefabricated glue is poured into and is placed in vacuum in moldIn drying box, it is concentrated and dried until product constant weight, demoulding is to get highly-breathable medical gel material.
The mass fraction of sodium hydroxide solution as described in step (1) is 5~10%, and the bath temperature in water-bath is 95~100 DEG C, constant temperature soaking time is 30~40min, and the mass fraction of hydrochloric acid is 5~8%.
Supersonic frequency in sonic oscillation instrument described in step (2) is 40~45kHz, and duration of oscillation is 50~60min.
For reaction kettle warming temperature described in step (3) to 190~210 DEG C, the isothermal reaction time is 2~3h, and vacuum is dryTemperature is 50~55 DEG C in dry case, and vacuum degree is 80~100Pa, and drying time is 2~3h.
The revolving speed of blender described in step (4) is 400~450r/min, and mixing time is 60~70min, micro-The power of wave furnace is 240~260W, and heating time is 3~5min, and the vacuum degree in vacuum oven is 80~100Pa, temperatureIt is 40~45 DEG C.
Temperature in household freezer described in step (5) is -35~-30 DEG C, and time of repose is 5~6h, and speed of agitator is2000~2200r/min, temperature are -25~-20 DEG C, and mixing time is 2~3h.
For reactor temperature temperature described in step (6) to 40~45 DEG C, the reaction time is 2~3h, revolving speed is 100~120r/min, temperature are 40~45 DEG C, and the reaction time is 60~80min, and the vacuum degree in vacuum oven is 80~100Pa,Temperature is 50~60 DEG C.
The method have the benefit that:
(1) Chinese aloe leaf is placed in lye by the present invention first impregnates, and is digested using cellulase to Chinese aloe leaf after immersion, soAfterwards using ferric trichloride as raw material, high-temperature water cooks to obtain reaction solid product, then the Chinese aloe leaf for reacting solid product and enzymatic hydrolysis is mixedIt closes, and reacting slurry is made with microwave heating, then freeze chitosan and mixed be incorporated in household freezer of other reagents, after freezingReacting slurry is added and is mixed to prepare mixed glue solution at low temperature, finally mix mixed glue solution with water and is concentrated and dried is obtained high saturatingGas medical gel material, the present invention, by dipping by lye boiling and cellulase degradation, make Chinese aloe leaf using Chinese aloe leaf as raw materialIn nutritional ingredient, plant fiber and cellulose separation, then ferric trichloride, sodium acetate, sodium citrate and ethylene glycol mixed highWarm water cooks to obtain nano ferriferrous oxide, and obtained nano ferriferrous oxide is mixed with ingredient each in aloe, adds after mixingEnter chitosan, covalent bond, hydrogen bond are generated by each nutriment in the magnetism of ferroso-ferric oxide institute band itself and aloe and dividesActive force adsorbs between son, and there are also chitosans to generate coupled action to metal oxide, makes ferroso-ferric oxide to gas chromatography shapeAt strong attraction, to generate microcosmic microsphere particle, microsphere particle helps to increase organic substance to extraneous contactSurface area makees the reparation of human epidermal cell to give full play to nutritional ingredient in the sterilizing effect and aloe of chitosanWith the formation of microballoon can also form more hole, enhance the gas permeability of gel rubber material；
(2) present invention first reacts chitosan under freezing conditions with urea and potassium hydroxide mixing, is made point using cryogenic freezingSubchain is rolled up, and adding sodium carboxymethylcellulose makes chitosan access carboxymethyl cellulose, by being had in carboxymethyl celluloseSome carboxyls, hydroxyl and each glucose make to be easier to produce between cellulose and chitosan to the intermolecular force of extraneous moleculeRaw suction-operated, to form the nanosphere centered on chitosan around chitosan surface is attached to, the formation of microballoon hasThe contact area for helping increase chitosan, enhances germicidal efficiency, while there are hole between microballoon, helps to increase gel rubber materialAir permeability effect.
Specific embodiment
It weighs the chopping of 300~400g Chinese aloe leaf to be placed in a beaker, be fallen with the sodium hydroxide solution that mass fraction is 5~10%Entering and impregnate Chinese aloe leaf in beaker, places the beaker in the water-bath that bath temperature is 95~100 DEG C, constant temperature impregnates 30~40min,It is cooled to room temperature after immersion, salt acid for adjusting pH value to the neutrality that mass fraction is 5~8% is added dropwise, solidliquid mixture is made；To above-mentionedThe cellulase of solidliquid mixture quality 2~4% is added in beaker, places the beaker in sonic oscillation instrument, is 40 in supersonic frequency50~60min is vibrated under conditions of~45kHz, and filtrate is obtained by filtration after oscillation, it is spare；According to parts by weight, 1.4 are weighed~In 1.7 parts of ferric trichlorides, 4.8~5.2 parts of sodium acetates, 0.4~0.6 part of sodium citrate and 80~90 parts of ethylene glycol investment reaction kettlesIt is uniformly mixed obtained mixed liquor, reaction kettle is warming up to 190~210 DEG C, filter residue is obtained by filtration after reaction in 2~3h of isothermal reaction,Being put into vacuum oven after being washed with distilled water 3~5 times in temperature is 50~55 DEG C, and vacuum degree is the condition of 80~100PaReaction solid product is made in 2~3h of lower drying；According to parts by weight, 3~5 parts of above-mentioned reaction solid products, 50~55 parts are weighedSpare filtrate, 1.0~1.2 parts of urea and 14~18 parts of distilled water are put into three-necked flasks, with blender with 400~450r/The revolving speed of min is mixed 60~70min and mixed emulsion is made, and three-necked flask is placed in micro-wave oven, power be 240~3~5min is heated under conditions of 260W, to be put into vacuum oven after heating with vacuum degree be 80~100Pa, temperature be 40~It is concentrated and dried under conditions of 45 DEG C until product constant weight, is made reacting slurry；According to parts by weight, 2~3 parts of chitosans, 6 are weighedIt is stirred evenly in~7 parts of potassium hydroxide powders, 20~22 parts of urea powders and 60~65 parts of distilled water investment beakers, beaker is set5~6h is stood under conditions of temperature is -35~-30 DEG C in household freezer, reactant is made, according to parts by weight, by 13~In 14 parts of above-mentioned reacting slurries, 20~22 parts of reactants and 1.5~1.8 parts of sodium carboxymethylcellulose investment beakers, turn in stirringSpeed be 2000~2200r/min and temperature be -25~-20 DEG C under conditions of stir 2~3h, be made mixed glue solution；It will be above-mentioned mixedIt closes glue to be placed in reaction kettle, increases reactor temperature to 40~45 DEG C, epoxy glue is added into reaction kettle after reacting 2~3hThe distilled water that 2.0~2.5 times of liquid quality reacts 60 under conditions of revolving speed is 100~120r/min and temperature is 40~45 DEG CPrefabricated glue is made in~80min, reaction, and it is 80 in vacuum degree in a vacuum drying oven that prefabricated glue, which is poured into juxtaposition in mold,~100Pa and temperature are concentrated and dried under conditions of being 50~60 DEG C until product constant weight, demoulding is to get highly-breathable medical gelMaterial.
It weighs the chopping of 300g Chinese aloe leaf to be placed in a beaker, is poured into beaker and soaked with the sodium hydroxide solution that mass fraction is 5%Stain Chinese aloe leaf places the beaker in the water-bath that bath temperature is 95 DEG C, and constant temperature impregnates 30min, is cooled to room temperature after immersion, dripsAdd salt acid for adjusting pH value to the neutrality that mass fraction is 5% that solidliquid mixture is made；Solidliquid mixture matter is added into above-mentioned beakerThe cellulase of amount 2%, places the beaker in sonic oscillation instrument, vibrates 50min under conditions of supersonic frequency is 40kHz, vibratesAfter filtrate is obtained by filtration, it is spare；According to parts by weight, 1.4 parts of ferric trichlorides, 4.8 parts of sodium acetates, 0.4 part of sodium citrate are weighedIt is uniformly mixed obtained mixed liquor in 80 parts of ethylene glycol investment reaction kettles, reaction kettle is warming up to 190 DEG C, isothermal reaction 2h, insteadShould after filter residue is obtained by filtration, being put into vacuum oven after being washed with distilled water 3 times in temperature is 50 DEG C, and vacuum degree is 80PaUnder the conditions of dry 2h reaction solid product is made；According to parts by weight, weigh 3 parts of above-mentioned reaction solid products, 50 parts it is spareIn filtrate, 1.0 parts of urea and 14 parts of distilled water investment three-necked flasks, it is mixed with blender with the revolving speed of 400r/minMixed emulsion is made in 60min, and three-necked flask is placed in micro-wave oven, 3min is heated under conditions of power is 240W, after heatingIt is concentrated and dried under conditions of being put into vacuum oven with vacuum degree is 80Pa, temperature is 40 DEG C until product constant weight, is made anti-Answer slurries；According to parts by weight, 2 parts of chitosans, 6 parts of potassium hydroxide powders, 20 parts of urea powders and 60 parts of distilled water are weighed to throwEnter in beaker and stir evenly, place the beaker in household freezer and stand 5h under conditions of temperature is -35 DEG C, reactant is made, pressesParts by weight meter is being stirred in 13 parts of above-mentioned reacting slurries, 20 parts of reactants and 1.5 parts of sodium carboxymethylcellulose investment beakersMix revolving speed be 2000r/min and temperature be -25 DEG C under conditions of stir 2h, be made mixed glue solution；Above-mentioned mixed glue solution is placed inIn reaction kettle, reactor temperature is increased to 40 DEG C, 2.0 times of mixed glue solution quality of distillation is added after reaction 2h into reaction kettleWater reacts 60min under conditions of revolving speed is 100r/min and temperature is 40 DEG C, and prefabricated glue is made in reaction, by prefabricated glueJuxtaposition in mold is poured into a vacuum drying oven, to be concentrated and dried under conditions of vacuum degree is 80Pa and temperature is 50 DEG C until producingObject constant weight, demoulding is to get highly-breathable medical gel material.
It weighs the chopping of 350g Chinese aloe leaf to be placed in a beaker, is poured into beaker and soaked with the sodium hydroxide solution that mass fraction is 7%Stain Chinese aloe leaf places the beaker in the water-bath that bath temperature is 97 DEG C, and constant temperature impregnates 35min, is cooled to room temperature after immersion, dripsAdd salt acid for adjusting pH value to the neutrality that mass fraction is 7% that solidliquid mixture is made；Solidliquid mixture matter is added into above-mentioned beakerThe cellulase of amount 3%, places the beaker in sonic oscillation instrument, vibrates 55min under conditions of supersonic frequency is 42kHz, vibratesAfter filtrate is obtained by filtration, it is spare；According to parts by weight, 1.6 parts of ferric trichlorides, 5.0 parts of sodium acetates, 0.5 part of sodium citrate are weighedIt is uniformly mixed obtained mixed liquor in 85 parts of ethylene glycol investment reaction kettles, reaction kettle is warming up to 200 DEG C, isothermal reaction 2.5h,Filter residue is obtained by filtration after reaction, being put into vacuum oven after being washed with distilled water 4 times in temperature is 52 DEG C, vacuum degree 90PaUnder conditions of dry 2.5h reaction solid product is made；According to parts by weight, weigh 4 parts of above-mentioned reaction solid products, 52 parts it is standbyIn filtrate, 1.1 parts of urea and 16 parts of distilled water investment three-necked flasks, it is mixed with blender with the revolving speed of 420r/minMixed emulsion is made in 65min, and three-necked flask is placed in micro-wave oven, 4min is heated under conditions of power is 250W, after heatingIt is concentrated and dried under conditions of being put into vacuum oven with vacuum degree is 90Pa, temperature is 42 DEG C until product constant weight, is made anti-Answer slurries；According to parts by weight, 2 parts of chitosans, 6 parts of potassium hydroxide powders, 21 parts of urea powders and 62 parts of distilled water are weighed to throwEnter in beaker and stir evenly, place the beaker in household freezer and stand 5.5h under conditions of temperature is -32 DEG C, reactant is made,According to parts by weight, 13 parts of above-mentioned reacting slurries, 21 parts of reactants and 1.7 parts of sodium carboxymethylcelluloses are put into beakers,Speed of agitator be 2100r/min and temperature be -22 DEG C under conditions of stir 2.5h, be made mixed glue solution；By above-mentioned mixed glue solutionIt is placed in reaction kettle, increases reactor temperature to 42 DEG C, 2.2 times of mixed glue solution quality are added into reaction kettle after reacting 2.5hDistilled water, react 70min under conditions of revolving speed is 110r/min and temperature is 42 DEG C, prefabricated glue is made in reaction, will be pre-Glue liquid pours into juxtaposition in mold and in a vacuum drying oven, is concentrated and dried under conditions of vacuum degree is 90Pa and temperature is 55 DEG CUntil product constant weight, demoulding is to get highly-breathable medical gel material.
It weighs the chopping of 400g Chinese aloe leaf to be placed in a beaker, be poured into beaker with the sodium hydroxide solution that mass fraction is 10%Chinese aloe leaf is impregnated, is placed the beaker in the water-bath that bath temperature is 100 DEG C, constant temperature impregnates 40min, is cooled to room after immersionTemperature is added dropwise salt acid for adjusting pH value to the neutrality that mass fraction is 8% and solidliquid mixture is made；It is mixed that solid-liquid is added into above-mentioned beakerThe cellulase for closing amount of substance 4%, places the beaker in sonic oscillation instrument, vibrates under conditions of supersonic frequency is 45kHzFiltrate is obtained by filtration in 60min after oscillation, spare；According to parts by weight, 1.7 parts of ferric trichlorides, 5.2 parts of sodium acetates, 0.6 are weighedIt is uniformly mixed obtained mixed liquor in part sodium citrate and 90 parts of ethylene glycol investment reaction kettles, reaction kettle is warming up to 210 DEG C, constant temperature3h is reacted, filter residue is obtained by filtration after reaction, being put into vacuum oven after being washed with distilled water 5 times in temperature is 55 DEG C, vacuumDegree dry obtained reaction solid product of 3h under conditions of being 100Pa；According to parts by weight, weigh 5 parts of above-mentioned reaction solid products,It is mixed with the revolving speed of 450r/min with blender in 55 parts of spare filtrates, 1.2 parts of urea and 18 parts of distilled water investment three-necked flasksIt closes stirring 70min and mixed emulsion is made, three-necked flask is placed in micro-wave oven, heats 5min under conditions of power is 260W,It is concentrated and dried under conditions of being put into vacuum oven after heating with vacuum degree is 100Pa, temperature is 45 DEG C up to product constant weight,Reacting slurry is made；According to parts by weight, 3 parts of chitosans, 7 parts of potassium hydroxide powders, 22 parts of urea powders and 65 parts of steamings are weighedIt is stirred evenly in distilled water investment beaker, places the beaker in household freezer and stand 6h under conditions of temperature is -30 DEG C, reaction is madeObject according to parts by weight puts into 14 parts of above-mentioned reacting slurries, 22 parts of reactants and 1.8 parts of sodium carboxymethylcelluloses in beakers,3h is stirred under conditions of speed of agitator is 2200r/min and temperature is -20 DEG C, mixed glue solution is made；By above-mentioned mixed glue solutionIt is placed in reaction kettle, increases reactor temperature to 45 DEG C, 2.5 times of mixed glue solution quality are added into reaction kettle after reacting 3hDistilled water reacts 80min under conditions of revolving speed is 120r/min and temperature is 45 DEG C, and prefabricated glue is made in reaction, will be prefabricatedGlue pours into juxtaposition in mold and in a vacuum drying oven, is concentrated and dried under conditions of vacuum degree is 100Pa and temperature is 60 DEG CUntil product constant weight, demoulding is to get highly-breathable medical gel material.
The highly-breathable medical gel material that comparative example is produced with Shaanxi company is as a comparison case to produced by the present inventionHighly-breathable medical gel material in highly-breathable medical gel material and comparative example carries out performance detection, testing result such as tableShown in 1:
Test method:
Expansion rate of water absorption test: the medical gel material in example 1~3 and comparative example is dried in vacuo, and is distinguished after dryWrite down weight.Medical gel material after drying is impregnated into 12h into the water, the weight of gel rubber material after water suction is calculated after 12h.Weight and the weight multiple of gel rubber material dry before water suction are as follows after water suction:
Sterilizing test: the medical gel material in example 1~3 and comparative example is used for the reparation of human epidermal cellIn, medical gel material is removed after a period of time, and measure the clump count of epidermis, obtain bacteriostasis rate.
Escherichia coli bacteriostasis rate, which is tested, carries out bacteriostasis property detection by the regulation of JC/T897-2002.
Staphylococcus aureus bacteriostasis rate number, which is tested, carries out bacteriostasis property detection by the regulation of JC/T897-2002.
Candida albicans bacteriostasis rate, which is tested, carries out performance detection by the regulation of GB/T20944.2-2007.
1 medical gel material property measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Weight multiple after water suction | 63 | 65 | 67 | 40 |
| Porosity (%) | 9.3 | 94 | 95 | 70 |
| Escherichia coli bacteriostasis rate (%) | 99.85 | 99.92 | 99.99 | 82.56 |
| Staphylococcus aureus bacteriostasis rate (%) | 99.78 | 99.88 | 99.99 | 81.25 |
| Candida albicans bacteriostasis rate (%) | 99.56 | 99.78 | 99.99 | 80.43 |
High, the biofacies according to weight multiple after the highly-breathable medical gel material water suction produced by the present invention of data among the aboveCapacitive and expansion rate of water absorption are high, and porosity is high, and good permeability, disinfection effect is good, all reach 99.99%, have wide answerUse prospect.