CN103405802A - Preparation method of polyurethane bandage with functions of sterilization and itch relief and bandage manufactured by method - Google Patents

Preparation method of polyurethane bandage with functions of sterilization and itch relief and bandage manufactured by method Download PDF

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Publication number
CN103405802A
CN103405802A CN2012102404960A CN201210240496A CN103405802A CN 103405802 A CN103405802 A CN 103405802A CN 2012102404960 A CN2012102404960 A CN 2012102404960A CN 201210240496 A CN201210240496 A CN 201210240496A CN 103405802 A CN103405802 A CN 103405802A
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itch
sterilizing
chitosan
parts
preparation
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CN103405802B (en
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王栋
陆莹
沈博强
胡修元
张新强
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Zhejiang Stange Sports Medical Technology Co ltd
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SHAOXING LIDE BIOTECHNOLOGY Co Ltd
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Abstract

The invention discloses a preparation method of a medical polyurethane bandage with the functions of sterilization and itch relief. The preparation method comprises the following steps of firstly preparing a polyurethane prepolymer and chitosan microspheres or chitosan quaternary ammonium salt with the functions of sterilization and itch relief, then uniformly coating the polyurethane prepolymer on base cloth, and coating chitosan microspheres or chitosan quaternary ammonium salt on the base cloth coated with the polyurethane prepolymer under the guiding of a guide drum. The bandage prepared by the method comprises a base material, the polyurethane prepolymer coated on the base material and the chitosan microspheres or chitosan quaternary ammonium salt with the functions of sterilization and itch relief, and therefore, compared with conventional immovable bandages, the bandage prepared by the method has the advantages of good shaping property, high strength, light weight, low cost and aesthetic property and can be used for effectively killing bacteria on the surfaces of skins so as to prevent the skins from swelling and itching and providing a dry comfortable environment for patients.

Description

The binder that the preparation method of sterilizing and itch-relieving polyurethane bandage and the method make
Technical field
The present invention relates to the medical and hygiene article technical field, especially relate to a kind of preparation method of medical polyurethane binder of the water chain extension with sterilizing and itch-relieving function, and the binder that utilizes the method to make.
Background technology
Early eighties, at first Bayer company proposes to apply base polyurethane prepolymer for use as on mesh fabric and makes binder, and this is great development of form in the orthopaedics therapy field.The using method of this binder is exactly that binder is first contacted with the water under room temperature, then be wound into patient's affected part, the base polyurethane prepolymer for use as be coated on base cloth can react with water the bandage hardening gradually by initial softness, after certain hour, form rigid material and fix patient's affected part, now binder has its shape of very high intensity and can not change again.Because this binder has the advantages such as lightweight, that intensity is high, the X ray permeability is good, in the extensive use of many medical departments.
But we find that polyurethane bandage product both domestic and external easily causes the allergic phenomenas such as red swelling of the skin pruritus in actual applications, because generally being used the number of plies, polyurethane bandage is the 5-8 layer, although breathability is better than tight plaster bandage, but in hot summer or for the skin sensitivity person, patient skin will have because the binder breathability is good not the phenomenon of pruritus redness to occur; Moreover the raw material costliness of existing polyurethane bandage, production cost is higher.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, a kind of preparation method with binder of sterilizing and itch-relieving function is provided, preparation method of the present invention is cheap for manufacturing cost, the medicine of the polyurethane bandage energy slow release sterilizing and itch-relieving of preparing, solve the puzzlements such as red and swollen pruritus that bring of patient because of skin sensitivity.
To achieve these goals, the present invention by the following technical solutions: a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving comprises the steps:
1) preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 100 parts of aromatic diisocyanates, stabilizing agent 0.1-5 part and silicone defoaming agent 0.5-5 part, after under 25-50 ℃, stirring 30min, the composition A that slowly adds 15-70 part, continue the composition B that dropwise adds 10-55 part after heated and stirred 30-120min, after reaction 1-3h, add catalyst 1-8 part, lubricant 3-10 part, continue heated and stirred 10-90min; Described composition A is that molecular weight is that polyether Glycols or the molecular weight of 800-1100 is the 300-600 polyether-tribasic alcohol, and described composition B is that molecular weight is the polyether Glycols of 1800-2200;
2) has the preparation of chitosan microball or the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
Preparation with chitosan microball of sterilizing and itch-relieving medicine:
A. 50 parts of chitosans being dissolved in to mass fraction is in the 0.5-15% acetum, is stirred to chitosan and dissolves fully, obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball;
B. taking chitosan microball 1-5 part of above-mentioned preparation, is 0.1-10% acetum stirring and dissolving with 10-50 part mass fraction, forms A liquid;
C. get sterilizing and itch-relieving medicine 0.5-2 part, dissolve by 5-20 part absolute ethyl alcohol and stirring, form B liquid;
D. get the B liquid 1-5 part in the c step, slowly at the uniform velocity splash in the A liquid of 10-20 part, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10-50% glutaraldehyde water solution 5-10 part, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function;
Preparation with chitosan quaternary ammonium salt of sterilizing and itch-relieving function:
A. in 10-50 part ethanol, acetone or isopropanol medium, adding 1-15 part mass fraction is that the sodium hydroxide of 10-30% or sodium carbonate are as acid binding agent, add quaternizing agent expoxy propane or N-Propyl Bromide 2-15 part, chitosan 5-40 part is carried out graft modification, obtains the chitosan quaternary ammonium salt material;
B. by above-mentioned chitosan quaternary ammonium salt material, with methanol and/or ethanol water washing, thereby, after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, dissolve with deionized water or distilled water, then be placed in bag filter in the distilled water desalination of dialysing;
C. dialyse after desalination concentrating under reduced pressure or normal pressure is directly concentrated to generate the concentrated solution of chitosan-containing quaternary ammonium salt 30%-80%, with dehydrated alcohol and/or acetone precipitation, go out the chitosan quaternary ammonium salt wet stock again, finally use dehydrated alcohol and/or washing with acetone chitosan quaternary ammonium salt wet stock, can obtain the chitosan quaternary ammonium product salt after drying;
3) contain the preparation of the polyurethane bandage of sterilizing and itch-relieving medicine
The base polyurethane prepolymer for use as made in step 1 is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving function chitosan microsphere or chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to chitosan microball or the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
As preferably, described catalyst is selected from dimethylethanolamine, organotin catalysts, triethylenediamine, dimethyl benzylamine, two (2,2-morpholine ethyl) ether, dimethylaminoethanol, the rare triamine of tetramethyl dipropyl, dimethyl diethanolamine, a kind of in the DIMAPA diisopropanol.
As preferably, described stabilizing agent is selected from a kind of in propionyl chloride, Benzenecarbonyl chloride., pyrovinic acid, maleic anhydride; Described lubricant is silicone lubricant or polyethylene glycol oxide.
As preferably, described aromatic diisocyanate is selected from 4,4'-methyl diphenylene diisocyanate, 2,4'-methyl diphenylene diisocyanate, 2,2'-methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, a kind of in the 4-vulcabond.
As preferably, described polyether Glycols is polypropylene glycol or polytetrahydrofuran diol.
As preferably, described composition A is that molecular weight is the polyether Glycols of 800-1100, and described composition B is that molecular weight is the polyether Glycols of 1800-2200, and the mass ratio of composition A and composition B is 1:0.57.
As preferably, described composition A is 63 parts.
As preferably, described sterilizing and itch-relieving medicine is selected from one or more the combination in chlorhexidine, amoxicillin, tetracycline, eucalyptus oil, Co tinctura indomethacinum, methyl salicylate, beclometasone.
The present invention also provides another technical scheme: a kind of binder that adopts above-mentioned preparation method to make, described binder comprise base material, are coated in the base polyurethane prepolymer for use as on base material, the chitosan microball that comprises the sterilizing and itch-relieving function or chitosan quaternary ammonium salt.
As preferably, the Unit Weight of described binder is 95-110g/m 2, cross direction elongation is 2.7-3.5%, the longitudinal tensile strain rate is 10-20%.
" aromatic series " in aromatic diisocyanate of the present invention can be any aromatic group with phenyl ring, because aromatic diisocyanate is mainly used in base polyurethane prepolymer for use as, and in the present invention, base polyurethane prepolymer for use as is a kind of excipient (" excipient "), be called again adjuvant.Aromatic group with phenyl ring can make aromatic diisocyanate have stronger physical arrangement, and then improves physical arrangement intensity and the hardness of base polyurethane prepolymer for use as.
Beneficial effect of the present invention:
1. binder preparation method of the present invention, technique is simple, cheap for manufacturing cost, it is the polyether diols of 1800-2200 or the trihydroxy polyethers that molecular weight is 300-600 that its polyethers adopts molecular weight, the polyether diols that is 800-100 with molecular weight combines, it is and easily obtains on the market medicine, easily manufactured, is applicable to output production.
2. utilize binder prepared by the method can offer the comfortable orthopaedics therapy condition of patient, wherein add the chitosan-containing quaternary ammonium salt or with the chitosan microball of sterilizing and itch-relieving medicine, after binder is wound into patient's affected part, chitosan quaternary ammonium salt or can effectively kill the antibacterial of skin surface from the sterilizing and itch-relieving medicine slowly released microsphere, prevent the red swelling of the skin pruritus, for the patient provides dry comfortable rehabilitation environment.In the method, chitosan quaternary ammonium salt is owing to containing-N +-positively charged, and bacterium surface is electronegative, the chitosan quaternary ammonium salt on the polyurethane bandage surface can effectively attract antibacterial, and hydrocarbyl group penetrates antibacterial simultaneously, reaches the effect of effective sterilization.
3. the binder for preparing of this method, owing to meeting before water the pliability that can keep base cloth, is met after water crosslinking solidifies and is had again high strength, so, than traditional immovable bandage, have that plasticity is good, intensity is high, has again lightweight, the inexpensive advantage such as attractive in appearance simultaneously.
The specific embodiment
In order to make those skilled in the art person better understand the present invention program, below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out to clear, complete description, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, should belong to the scope of protection of the invention.
Embodiment 1
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,2.5 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 0.5 part of Benzenecarbonyl chloride. stabilizing agent and silicone defoaming agents, after under 45 ℃, stirring 30min, slowly adding molecular weight is 20 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 60min dropwise to add molecular weight is 35 parts of the polypropylene glycols of 1800-2200, after reaction 2h, add 3 parts of catalyst dimethylethanolamines, 5 parts of lubricant silicone oil, after continuing heated and stirred 15min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 5% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 5 parts of the chitosan microballs of above-mentioned preparation, is 0.1% acetum stirring and dissolving with 30 parts of mass fractions, forms A liquid; Get 1 part of sterilizing and itch-relieving medicine amoxicillin, dissolve by 10 parts of absolute ethyl alcohol and stirring, form B liquid; Get 2 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 12 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 5 parts of 10% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function;
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, the thread base cloth of Polyester Yarns first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 2
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,3.2 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1.8 parts of Benzenecarbonyl chloride .s and silicone defoaming agents, after under 30 ℃, stirring 30min, slowly adding molecular weight is 18 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 90min dropwise to add molecular weight is 40 parts of the polypropylene glycols of 1800-2200, after reaction 2.5h, add catalyst triethylenediamine 1-8 part, silicone lubricant 3-10 part, after continuing heated and stirred 50min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 10 parts of medium-acetones, add 5 parts of mass fractions be 30% sodium hydroxide as acid binding agent, add 5 parts of quaternizing agent expoxy propane, 20 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.By this material, be that the washing of 10% methanol aqueous solution is removed the salinity in material with part with mass fraction, thereby, after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, dissolve with distilled water, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination, normal pressure is directly concentrated to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then uses enough acetone precipitations, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with absolute ethanol washing, then drying can obtain the chitosan quaternary ammonium product salt.
3. contain the preparation of water chain extension polyurethane bandage of the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove of the chitosan quaternary ammonium salt that splendid attire contains the sterilizing and itch-relieving function, the spun polyester thread base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 3
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,3.5 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 4.2 parts of propionyl chlorides and silicone defoaming agents, after under 20 ℃, stirring 30min, slowly adding molecular weight is 30 parts of 300-600 polyether-tribasic alcohols, continuing after heated and stirred 70min dropwise to add molecular weight is 10 parts of the polytetrahydrofuran diols of 1800-2200, reaction adds 3 parts of dibutyltin dilaurates in organotin catalysts after 1.5h, 5 parts of silicone lubricant, continue heated and stirred 45min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
50 parts of chitosans are dissolved in 15% acetum, are stirred to fully and dissolve, obtain centrifugal condensing after chitosan solution.Decompress filter after standing 36h, dry and obtain chitosan microball with absolute ethanol washing to neutral rearmounted thermostatic drying chamber.Taking 2 parts of the chitosan microballs of above-mentioned preparation, is 0.8% acetum stirring and dissolving with 25 parts of mass fractions, forms A liquid.Get 1.5 parts of sterilizing and itch-relieving medicine tetracyclines, dissolve by 20 parts of absolute ethyl alcohol and stirring, form B liquid.4 parts of B liquid are slowly at the uniform velocity splashed in 15 parts of A liquid, and vigorous stirring 10min, form C liquid.In C liquid, drip 7 parts of 20% glutaraldehyde water solutions, centrifugal sedimentation after crosslinking curing 12h, relaunder precipitate to be drying to obtain the chitosan microball with sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 4
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,0.9 part of 100 parts of 4'-methyl diphenylene diisocyanates, 3.8 parts of pyrovinic acids and silicone defoaming agent, after under 40 ℃, stirring 80min, slowly adding molecular weight is 45 parts of 300-600 polyether-tribasic alcohols, continuing after heated and stirred 30min dropwise to add molecular weight is 25 parts of the polypropylene glycols of 1800-2200, after reaction 3h, add 3.5 parts of catalyst dimethyl benzylamines, 6 parts of profit silicone oil lubrication prescription, continue heated and stirred 65min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 9% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 3 parts of chitosan microballs, is 1% acetum stirring and dissolving with 40 parts of mass fractions, forms A liquid;
Get 1.5 parts of sterilizing and itch-relieving medicine eucalyptus oils, dissolve by 18 parts of absolute ethyl alcohol and stirring, form B liquid; Get 3 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 15 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 7 parts of 20% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 5
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,4 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 0.7 part of pyrovinic acid and silicone defoaming agents, after under 45 ℃, stirring 30min, slowly adding molecular weight is 63 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 30min dropwise to add molecular weight is 35.91 parts of the polypropylene glycols of 1800-2200, after reaction 1h45min, add catalyst two (2,2-morpholine ethyl) ether is 5 parts, 6 parts of silicone lubricant, continue heated and stirred 10min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 0.5% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 4.5 parts of chitosan microballs, is 0.9% acetum stirring and dissolving with 18 parts of mass fractions, forms A liquid;
Get 2 parts of sterilizing and itch-relieving medicaments compound indomethacin tinctures, dissolve by 15 parts of absolute ethyl alcohol and stirring, form B liquid; Get 3 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 15 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 6.5 parts of 23% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 6
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,100 parts of 2'-methyl diphenylene diisocyanates, maleic anhydride 0.1-5 part and silicone defoaming agent 0.5-5 part, after under 25-50 ℃, stirring 30min, slowly adding molecular weight is 55 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 30min dropwise to add molecular weight is 35 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 1h45min, add 5 parts of catalyst dimethylaminoethanols, 3 parts of polyethylene glycol oxides, continue heated and stirred 15min, obtain base polyurethane prepolymer for use as.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 0.5% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 3.5 parts of chitosan microballs, is 0.2% acetum stirring and dissolving with 40 parts of mass fractions, forms A liquid;
Get 0.5 part of 0.8 part of sterilizing and itch-relieving medicine methyl salicylate and eucalyptus oil, dissolve by 18 parts of absolute ethyl alcohol and stirring, form B liquid; Get 5 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 18 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10 parts of 23% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 7
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,2 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 5 parts of maleic anhydrides and silicone defoaming agents, after under 40 ℃, stirring 30min, slowly adding molecular weight is 50 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 40min dropwise to add molecular weight is 10 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 1h15min, add 7 parts of the rare triamines of catalyst tetramethyl dipropyl, 10 parts of silicone lubricant, continue heated and stirred 35min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 20 parts of isopropanol mediums, add 8 parts of mass fractions be 30% sodium carbonate as acid binding agent, 10 parts of quaternizing agent N-Propyl Bromides, 15 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.This material is removed to the salinity in material with the methanol aqueous solution washing that mass fraction is 20% with part, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, use deionized water dissolving, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination concentrating under reduced pressure to be to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then precipitates with enough dehydrated alcohol, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with absolute ethanol washing, then drying can obtain the chitosan quaternary ammonium product salt;
3. contain the preparation of water chain extension polyurethane bandage of the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove of the chitosan quaternary ammonium salt that splendid attire contains the sterilizing and itch-relieving function, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 8
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,3.8 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1.8 parts of maleic anhydrides and silicone defoaming agents, after under 35 ℃, stirring 30min, slowly adding molecular weight is 60 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 120min dropwise to add molecular weight is 25 parts of the polypropylene glycols of 1800-2200, after reaction 2.5h, add 4 parts of catalyst dimethyl diethanolamine, 7 parts of polyethylene glycol oxides, continue heated and stirred 15min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 13% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 2 parts of the chitosan microballs of above-mentioned preparation, is 8% acetum stirring and dissolving with 25 parts of mass fractions, forms A liquid;
Get 1.5 parts of sterilizing and itch-relieving medicine chlorhexidines, dissolve by 10 parts of absolute ethyl alcohol and stirring, form B liquid; Get 2 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 10 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10 parts of 15% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 9
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,5 parts of 100 parts of 2'-methyl diphenylene diisocyanates, 3 parts of Benzenecarbonyl chloride. stabilizing agents and silicone defoaming agents, after under 45 ℃, stirring 30min, slowly adding molecular weight is 55 parts of 300-600 polyether-tribasic alcohols, continuing after heated and stirred 90min dropwise to add molecular weight is 45 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 2h, add 7 parts of catalyst DIMAPA diisopropanols, 10 parts of polyethylene glycol oxides, continue heated and stirred 85min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 5% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 5 parts of the chitosan microballs of above-mentioned preparation, is 0.1% acetum stirring and dissolving with 30 parts of mass fractions, forms A liquid;
Get 1 part of sterilizing and itch-relieving medicine amoxicillin, dissolve by 10 parts of absolute ethyl alcohol and stirring, form B liquid; Get 2 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 12 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10% glutaraldehyde water solution 5-10 part, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 10
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add Toluene-2,4-diisocyanate, 3.2 parts of 100 parts of 4-vulcabond, 1.8 parts of propionyl chloride stabilizing agents and silicone defoaming agents, after under 30 ℃, stirring 30min, slowly adding molecular weight is 18 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 110min dropwise to add molecular weight is 40 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 1.5h, add catalyst triethylenediamine 1-8 part, silicone lubricant 3-10 part, continue heated and stirred 90min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 13% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 2 parts of the chitosan microballs of above-mentioned preparation, is 8% acetum stirring and dissolving with 25 parts of mass fractions, forms A liquid;
Get 1.5 parts of sterilizing and itch-relieving medicine chlorhexidines, dissolve by 10 parts of absolute ethyl alcohol and stirring, form B liquid; Get 2 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 10 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10 parts of 15% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 11
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,3.5 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 4.2 parts of aromatic series Benzenecarbonyl chloride. stabilizing agents and silicone defoaming agents, after under 20 ℃, stirring 30min, slowly adding molecular weight is 30 parts of 300-600 polyether-tribasic alcohols, continuing after heated and stirred 100min dropwise to add molecular weight is 10 parts of the polypropylene glycols of 1800-2200, after reaction 1h, add 3 parts of organotin catalysts such as dibutyltin dilaurates, 5 parts of polyethylene glycol oxides, continue heated and stirred 90min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
50 parts of chitosans are dissolved in 15% acetum, are stirred to fully and dissolve, obtain centrifugal condensing after chitosan solution.Decompress filter after standing 36h, dry and obtain chitosan microball with absolute ethanol washing to neutral rearmounted thermostatic drying chamber.Taking 2 parts of the chitosan microballs of above-mentioned preparation, is 0.8% acetum stirring and dissolving with 25 parts of mass fractions, forms A liquid.
Get 1.5 parts of sterilizing and itch-relieving medicine tetracyclines, with by 20 parts of absolute ethyl alcohol and stirring, dissolving, form B liquid.4 parts of B liquid are slowly at the uniform velocity splashed in 15 parts of A liquid, and vigorous stirring 10min, form C liquid.In C liquid, drip 7 parts of 20% glutaraldehyde water solutions, centrifugal sedimentation after crosslinking curing 12h, relaunder precipitate to be drying to obtain the chitosan microball with sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 12
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,0.9 part of 4'-methyl diphenylene diisocyanate MDI100 part, 3.8 parts of aromatic series Benzenecarbonyl chloride. stabilizing agents and silicone defoaming agent, after under 40 ℃, stirring 30min, slowly adding molecular weight is 45 parts of 300-600 polypropylene glycols, continuing after heated and stirred 90min dropwise to add molecular weight is 25 parts of the polypropylene glycols of 1800-2200, after reaction 1h45min, add 3.5 parts of catalyst dimethyl benzylamines, 6 parts of profit silicone oil lubrication prescription, continue heated and stirred 45min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 9% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 3 parts of chitosan microballs, is 1% acetum stirring and dissolving with 40 parts of mass fractions, forms A liquid;
Get 1.5 parts of sterilizing and itch-relieving medicine eucalyptus oils, dissolve by 18 parts of absolute ethyl alcohol and stirring, form B liquid; Get 3 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 15 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 7 parts of 20% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 13
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,3 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1 part of propionyl chloride and silicone defoaming agents, after under 40 ℃, stirring 30min, slowly adding molecular weight is 50 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 45min dropwise to add molecular weight is 10 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 1h15min, add catalyst two (2,2-morpholine ethyl) ether is 7 parts, 10 parts of silicone lubricant, continue heated and stirred 30min.
2. the preparation that has the chitosan microball of sterilizing and itch-relieving medicine
It is in 2% acetum that 50 parts of chitosans are dissolved in to mass fraction, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball; Taking 3 parts of chitosan microballs, is 1.5% acetum stirring and dissolving with 15 parts of mass fractions, forms A liquid;
Get 1 part of 2 parts of sterilizing and itch-relieving medicine beclometasones and chlorhexidine, dissolve by 20 parts of absolute ethyl alcohol and stirring, form B liquid; Get 5 parts of B liquid, slowly at the uniform velocity splash in the A liquid of 20 parts, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10 parts of 50% glutaraldehyde water solutions, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving medicine chitosan microball
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan microball with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 14
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,4.8 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1.8 parts of maleic anhydrides and silicone defoaming agents, after under 35 ℃, stirring 30min, slowly adding molecular weight is 60 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 120min dropwise to add molecular weight is 25 parts of the polypropylene glycols of 1800-2200, after reaction 2.5h, add 4 parts of catalyst maleic anhydrides, 7 parts of polyethylene glycol oxides, continue heated and stirred 10min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
3. in 40 parts of ethanol mediums, add 15 parts of mass fractions be 20% sodium hydroxide as acid binding agent, add 10 parts of quaternizing agent N-Propyl Bromides, 30 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.This material is removed to the salinity in material with the methanol aqueous solution washing that mass fraction is 5% with part, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, with deionized water or distilled water, dissolve, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination concentrating under reduced pressure to be to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then precipitates with enough dehydrated alcohol, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with absolute ethanol washing, then drying can obtain the chitosan quaternary ammonium product salt.
4. contain the preparation of water chain extension polyurethane bandage of the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving function chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 15
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,4 '-5 parts of 100 parts of methyl diphenylene diisocyanates, 3 parts of Benzenecarbonyl chloride. stabilizing agents and silicone defoaming agents, after under 45 ℃, stirring 30min, slowly adding molecular weight is 55 parts of 300-600 polyether-tribasic alcohols, continuing after heated and stirred 90min dropwise to add molecular weight is 45 parts of the polypropylene glycols of 1800-2200, after reaction 2h, add 5 parts of catalyst DIMAPA diisopropanols, 10 parts of polyethylene glycol oxides, continue heated and stirred 80min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 35 parts of medium-acetones, add 15 parts of mass fractions be 25% sodium hydroxide as acid binding agent, add 10 parts of quaternizing agent N-Propyl Bromides, 30 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.This material is removed to the salinity in material with the methanol aqueous solution washing that mass fraction is 5% with part, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, with deionized water or distilled water, dissolve, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination concentrating under reduced pressure to be to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then precipitates with enough dehydrated alcohol, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with absolute ethanol washing, then drying can obtain the chitosan quaternary ammonium product salt.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving function chitosan quaternary ammonium salt
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving function chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 16
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,3.2 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1.8 parts of Benzenecarbonyl chloride .s and silicone defoaming agents, after under 30 ℃, stirring 30min, slowly adding molecular weight is 18 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 100min dropwise to add molecular weight is 40 parts of the polypropylene glycols of 1800-2200, after reaction 2.5h, add catalyst triethylenediamine 1-8 part, silicone lubricant 3-10 part, continue heated and stirred 50min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 10 parts of medium-acetones, add 8 parts of mass fractions be 30% sodium carbonate as acid binding agent, add 5 parts of quaternizing agent expoxy propane, 20 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.By this material, be that the washing of 10% methanol aqueous solution is removed the salinity in material with part with mass fraction, thereby, after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, dissolve with distilled water, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination, normal pressure is directly concentrated to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then uses enough acetone precipitations, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with washing with acetone, then drying can obtain the chitosan quaternary ammonium product salt.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving function chitosan quaternary ammonium salt
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving medicine chitosan microball, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to chitosan microball or the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 17
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 2,3.2 parts of 100 parts of 4'-methyl diphenylene diisocyanates, 1.8 parts of Benzenecarbonyl chloride .s and silicone defoaming agents, after under 30 ℃, stirring 30min, slowly adding molecular weight is 18 parts of the polytetrahydrofuran diols of 800-1100, continuing after heated and stirred 100min dropwise to add molecular weight is 40 parts of the polypropylene glycols of 1800-2200, after reaction 2.5h, add catalyst triethylenediamine 1-8 part, silicone lubricant 3-10 part, continue heated and stirred 50min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 30 parts of isopropanol mediums, add 10 parts of mass fractions be 25% sodium hydroxide as acid binding agent, add 10 parts of quaternizing agent expoxy propane, 30 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.This material is removed to the salinity in material with the methanol aqueous solution washing that mass fraction is 5% with part, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, with deionized water or distilled water, dissolve, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination concentrating under reduced pressure to be to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then uses enough acetone precipitations, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with washing with acetone, then drying can obtain the chitosan quaternary ammonium product salt.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving function chitosan quaternary ammonium salt
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving function chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
Embodiment 18
1. the preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 4,4 '-3 parts of 100 parts of methyl diphenylene diisocyanates, 1 part of propionyl chloride and silicone defoaming agents, after under 40 ℃, stirring 30min, slowly adding molecular weight is 50 parts of the polypropylene glycols of 800-1100, continuing after heated and stirred 45min dropwise to add molecular weight is 10 parts of the polytetrahydrofuran diols of 1800-2200, after reaction 1h15min, add catalyst two (2,2-morpholine ethyl) ether is 7 parts, 10 parts of silicone lubricant, continue heated and stirred 30min.
2. the preparation that has the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
In 40 parts of isopropanol mediums, add 15 parts of mass fractions be 20% sodium carbonate as acid binding agent, add 10 parts of quaternizing agent expoxy propane, 35 parts of chitosans carry out graft modification, obtain the chitosan quaternary ammonium salt material.This material is removed to the salinity in material with the methanol aqueous solution washing that mass fraction is 5% with part, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, with deionized water or distilled water, dissolve, then be placed in bag filter in the distilled water desalination of dialysing.After the dialysis desalination concentrating under reduced pressure to be to generate the concentrated solution of chitosan-containing quaternary ammonium salt, then precipitates with enough dehydrated alcohol, precipitate is obtained to the chitosan quaternary ammonium salt wet stock with absolute ethanol washing, then drying can obtain the chitosan quaternary ammonium product salt.
3. contain the preparation of the water chain extension polyurethane bandage of sterilizing and itch-relieving function chitosan quaternary ammonium salt
1. the base polyurethane prepolymer for use as made in is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and the B groove that splendid attire contains sterilizing and itch-relieving function chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.

Claims (10)

1. the preparation method with medical polyurethane binder of sterilizing and itch-relieving function, is characterized in that: comprise the steps:
1) preparation of base polyurethane prepolymer for use as
In the four-hole reactor that passes into High Purity Nitrogen with agitator, thermometer, add 100 parts of aromatic diisocyanates, stabilizing agent 0.1-5 part and silicone defoaming agent 0.5-5 part, after under 25-50 ℃, stirring 30min, the composition A that slowly adds 15-70 part, continue the composition B that dropwise adds 10-55 part after heated and stirred 30-120min, after reaction 1-3h, add catalyst 1-8 part, lubricant 3-10 part, continue heated and stirred 10-90min; Described composition A is that molecular weight is that polyether Glycols or the molecular weight of 800-1100 is the 300-600 polyether-tribasic alcohol, and described composition B is that molecular weight is the polyether Glycols of 1800-2200;
2) has the preparation of chitosan microball or the chitosan quaternary ammonium salt of sterilizing and itch-relieving function
Preparation with chitosan microball of sterilizing and itch-relieving medicine:
A. 50 parts of chitosans being dissolved in to mass fraction is in the 0.5-15% acetum, is stirred to fully and dissolves, and obtains centrifugal condensing after chitosan solution; Decompress filter after standing 36h, dry with absolute ethanol washing to neutral rearmounted thermostatic drying chamber, obtains chitosan microball;
B. taking chitosan microball 1-5 part of above-mentioned preparation, is 0.1-10% acetum stirring and dissolving with 10-50 part mass fraction, forms A liquid;
C. get sterilizing and itch-relieving medicine 0.5-2 part, dissolve by 5-20 part absolute ethyl alcohol and stirring, form B liquid;
D. get the B liquid 1-5 part in the c step, slowly at the uniform velocity splash in the A liquid of 10-20 part, vigorous stirring 10min, form C liquid; In C liquid, dripping mass fraction is 10-50% glutaraldehyde water solution 5-10 part, and centrifugal sedimentation after crosslinking curing 12h, relaunder drying by precipitate, must have the chitosan microball of sterilizing and itch-relieving function; Preparation with chitosan quaternary ammonium salt of sterilizing and itch-relieving function:
A. in 10-50 part ethanol, acetone or isopropanol medium, adding 1-15 part mass fraction is that the sodium hydroxide of 10-30% or sodium carbonate are as acid binding agent, add quaternizing agent expoxy propane or N-Propyl Bromide 2-15 part, chitosan 5-40 part is carried out graft modification, obtains the chitosan quaternary ammonium salt material;
B. by above-mentioned chitosan quaternary ammonium salt material, with mass fraction, be methanol and/or the ethanol water washing of 5-30%, thereby after obtaining the solid material that contains n-trimethyl chitosan chloride of partial deionization, dissolve with deionized water or distilled water, then be placed in bag filter in the distilled water desalination of dialysing;
C. dialyse after desalination concentrating under reduced pressure or normal pressure is directly concentrated to generate the concentrated solution of chitosan-containing quaternary ammonium salt, with enough dehydrated alcohol and/or acetone precipitation, go out the chitosan quaternary ammonium salt wet stock again, finally use dehydrated alcohol and/or washing with acetone chitosan quaternary ammonium salt wet stock, can obtain the chitosan quaternary ammonium product salt after drying;
3) contain the preparation of the polyurethane bandage of sterilizing and itch-relieving function
The base polyurethane prepolymer for use as made in step 1 is warmed up to 55 ℃, the air moisture content lower than 10% nitrogen protection environment under, adopt the double flute that band is heated to contain liquid, be respectively the A groove of splendid attire base polyurethane prepolymer for use as and chitosan microball that splendid attire contains the sterilizing and itch-relieving function or the B groove of chitosan quaternary ammonium salt, base cloth first evenly is coated in base polyurethane prepolymer for use as on base cloth through the A groove, the base cloth that is coated with base polyurethane prepolymer for use as passes through the B groove again under the guiding of guide, the base cloth that scribbles base polyurethane prepolymer for use as is carried out to functionalization, evenly adhere to chitosan microball or the chitosan quaternary ammonium salt with sterilizing and itch-relieving function, again at work feed, after the PROCESS FOR TREATMENT such as roll-in, carry out rolling, shear and with Aluminum-plastic composite bag, pack again.
2. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described catalyst is selected from dimethylethanolamine, organotin catalysts, triethylenediamine, dimethyl benzylamine, two (2,2-morpholine ethyl) ether, dimethylaminoethanol, the rare triamine of tetramethyl dipropyl, the dimethyl diethanolamine, a kind of in the DIMAPA diisopropanol.
3. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1 is characterized in that: described stabilizing agent is selected from a kind of in propionyl chloride, Benzenecarbonyl chloride., pyrovinic acid, maleic anhydride;
Described lubricant is silicone lubricant or polyethylene glycol oxide.
4. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described aromatic diisocyanate is selected from 4,4'-methyl diphenylene diisocyanate, 2,4'-methyl diphenylene diisocyanate, 2,2'-methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, a kind of in the 4-vulcabond.
5. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described polyether Glycols is polypropylene glycol or polytetrahydrofuran diol.
6. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described composition A is that molecular weight is the polyether Glycols of 800-1100, described composition B is that molecular weight is the polyether Glycols of 1800-2200, and the mass ratio of composition A and composition B is 1:0.57.
7. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1, it is characterized in that: described composition A is 63 parts.
8. a kind of preparation method with medical polyurethane binder of sterilizing and itch-relieving function according to claim 1 is characterized in that: described sterilizing and itch-relieving medicine is selected from one or more the combination in chlorhexidine, amoxicillin, tetracycline, eucalyptus oil, Co tinctura indomethacinum, methyl salicylate, beclometasone.
9. the binder made according to the described preparation method of any one in claim 1-8 is characterized in that: described binder comprises base material, is coated in the base polyurethane prepolymer for use as on base material, the chitosan microball that comprises the sterilizing and itch-relieving function or chitosan quaternary ammonium salt.
10. binder according to claim 9, it is characterized in that: the Unit Weight of described binder is 95-110g/m 2, cross direction elongation is 2.7-3.5%, the longitudinal tensile strain rate is 10-20%.
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CN109880052A (en) * 2019-03-20 2019-06-14 亳州科蔚科技服务有限公司 A kind of medical bandage coating preparation method of polyurethane resin compound material
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CN113152115B (en) * 2021-04-22 2023-08-04 宁波因天之序生物科技有限公司 Medical orthopedic bandage and preparation method thereof

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