Background technology
Due to the skin injury that the reasons such as wound, burn and skin ulceration cause, the a series of problem of body can be caused, such as bacteriological infection, metabolism aggravation, moisture and protein excessively runs off, endocrine and immune system dysfunction etc., serious possible threat to life.Therefore, after skin injury, usually need to adopt the succedaneum medical dressing of skin to protect wound, prevent traumatic infection and serious dehydration, provide the moist environment being beneficial to wound healing, wound healing.In wound healing process, use medical dressing can form a physical barriers, stop dust, antibacterial etc. to enter wound, be convenient to wound care, promote wound healing.
In recent decades, the proposition theoretical along with wound surface " moistening healing " and the development of biomaterial, new pattern compress particularly new polyurethane dressing constantly occurs.Tradition Wound dressing (as gauze, Cotton Gossypii) etc. has many shortcomings: easily breed bacteria, and wound fluid easily forms crust together with dry dermal tissue, hinders epithelization; Simultaneously wound surface easily and dressing adhesion, changes dressings when uncovering and cause pain, bring secondary insult.New polyurethane dressing can keep the moistening of wound surface, controls steam permeating rate, and resists the intrusion of antibacterial; Its spongy porous laminated structure is conducive to the discharge of wound secretion, promotes the healing of wound tissue; Use and feel comfortable; There is excellent biocompatibility, without aberration inducing effect, without anaphylaxis; Toxicity test meets medical requirement; Have excellent toughness and elasticity, good processability, the plurality of advantages such as processing mode is various, are therefore used widely in the field such as Wound dressing and organizational project.
The construction features of polyurethanes foam self enables the intrusion generally suppressing extraneous antibacterial, the transudate of wound surface can be absorbed in a large number, however, its part that still comes with some shortcomings, such as, can not suppress or kill the entrained antibacterial of wound surface itself or virus, can not long-acting bacteriostatic etc.In order to make up deficiency in this respect, normally in the polyurethane foam of having synthesized, introduce physiologically active material or antibacterial, Fungicidal substance, adopt the method for physical blending or surface-coated, prepare composite polyurethane foam dressing, reach antibacterial and the effect of sterilization, the method can be improved polyurethane foam dressing according to actual needs, but bactericidal effect is limited.
In addition to the method described above, antibacterial or mildew-resistant foam dressing can also be gone out by adding one or more anti-infective drugs in the synthesizing formula of preparation technology, thus reach the effect of anti-bacteria or mycete breeding.The antibacterial polyurethane foam dressing one-shot forming of this method gained, do not need to carry out secondary operations, save time material-saving, reduces costs.The kind of antibacterial is a lot, comprises aseptic antibacterial and the large class of organic antibacterial agent two.In inorganic antiseptic, antibacterial effect is silver-series antibacterial agent preferably, and have the advantage that thermostability is higher, but cost is high, consumption is relatively large, and easy to change; Synthesis organic antibacterial has the features such as quick-acting, anti-mold effect is excellent, but the feature such as it is poor to have thermostability, and duration of efficacy is short, easily separates out, and safety is low.Such as, Chinese patent CN 103467702A discloses a kind of preparation method of antimicrobial form flexible polyurethane foam, a, add the polyether polyol N330 and 1 of metering in a kettle., 4-butanediol, the dibutyl tin laurate of catalytic amount, tripolycyanamide, nitrogen is full of or noble gas is protected in still, heat 40 ~ 60 DEG C, fully stir 6 ~ 8 hours, be cooled to 25 DEG C; Add polyisocyanate, silicone oil, triethylamine, nano zine oxide, suitable quantity of water in b, the product that obtains in step a, high-speed stirred is to foaming; When c, a large amount of white foam to appear, it is injected mould immediately, ripening 60 ~ 150 minutes at 40 ~ 60 DEG C, the demoulding, obtains flexible polyurethane foam plastic product.In the invention, using inorganic nano zinc oxide as antibacterial, prepare antimicrobial form flexible polyurethane foam by above-mentioned technique.Although this antimicrobial form flexible polyurethane foam has antibacterial effect, cannot realize long-acting bacteriostatic, and the cost of antibacterial is high, consumption is large.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, provide a kind of surface through plasma modification can organic polyurethane foam dressing and preparation method thereof of long-acting bacteriostatic.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of organic polyurethane foam dressing, is made up of the raw material of following weight parts proportioning: polyether polyol 40 ~ 60 parts, chain extender 15 ~ 20 parts, foaming agent 2 ~ 4 parts, 1 ~ 5 part, surfactant, catalyst 1 ~ 5 part, antibacterial 0.1 ~ 1.0 part, isocyanates 20 ~ 150 parts, pure water 1 ~ 3 part.
Prepare a method for described organic polyurethane foam dressing, comprise the following steps:
1. take the polyether polyol of described weight, chain extender, foaming agent, surfactant, catalyst, antibacterial and pure water respectively, in room temperature, stir 50 ~ 60s under the condition of 4000r/min, make mixed liquor;
2. the isocyanates taking described weight joins in the mixed liquor that 1. step prepared, and continue stirring 10 ~ 30s, and be incubated 30 ~ 50 minutes at 40 ~ 50 DEG C, obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, gets product.
Further, described polyether polyol be common polyether polyhydric alcohol and modified polyether polylol with the mixture of 1:1 ~ 10 weight, described modified polyether polylol is the one in styrene type, acrylonitrile type, methyl methacrylate type grafted polyether polyol.
Further, described chain extender is ethylenediamine.
Further, described foaming agent is the one in pentane, dichloromethane, isceon, hexane.
Further, described surfactant is organosilicone surfactants.
Further, described catalyst is the one in ferrocene, 1,8-diazabicylo 11 carbon-7-alkene, triethylene diamine, stannous 2-ethylhexoate, described catalyst preferably stannous 2-ethylhexoate.
Further, described antibacterial is the one in poly (hexamethylene), triclosan, chlorhexidine gluconate, chitosan.
Further, described isocyanates is hexamethylene diisocyanate, 4, the one in 4 '-'-diphenylmethane diisocyanate, toluene di-isocyanate(TDI), Isosorbide-5-Nitrae-cyclohexane diisocyanate.
Further, step 3. described in the condition of plasma surface modification process be: working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:1.5 ~ 6, and processing power is 20 ~ 2000w, and the processing time is 10 ~ 200s.
Beneficial effect of the present invention is as follows: compared with prior art, organic polyurethane foam dressing of the present invention and preparation method thereof, with polyether polyol and isocyanates for primary raw material, at chain extender, foaming agent, surfactant, the multiple auxiliary agent of catalyst, and under the combined effect of antibacterial, the polyurethane foam with bacteria resistance function is prepared by simple technique, and by gained polyurethane foam through plasma surface modification process, on antibacterial polyurethane foamed material surface, add one plasma rete as rate limiting barrier, control the release rate of medicine, the plasma membrane formed, is equivalent to an overcoat of material surface, does not affect the characteristic sum mechanical property of material itself completely, noble gas or hydrogen are as non-reacted plasma, after surface of polymer material is bombarded, the free radical that surface produces occurs crosslinked, by crosslinked for formation rete, not only change the free energy of material surface, but also oozing out of material internal pore former and medicine can be reduced, medicine release rate is reduced.
The present invention uses Cement Composite Treated by Plasma polyurethane foam surface under cryogenic, antipathogenic composition wherein can be made to reach the effect of slow release, thus make product have the feature of long-acting bacteriostatic under the prerequisite not affecting absorbent; Simultaneously after Cement Composite Treated by Plasma, polyurethane foam surface apertures reduces, and wound tissue not easily infiltrates foam inside, and product is adhesion wound not easily, and possesses certain anti-leakage function.Foam dressing prepared by the present invention and wound surface compliance are good, soft comfortable, and preparation technology is simple, easy to operate, treatment effect good, is applicable to suitability for industrialized production.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.02 × 10
-2~ 1.57 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 4 days.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment one
The organic polyurethane foam dressing of the present invention, is made up of the raw material of following weight parts proportioning: common polyether polyhydric alcohol 20 parts, styrene type grafted polyether polyol 20 parts, ethylenediamine 15 parts, pentane 2 parts, polymethyl siloxane-copolyether 1 part, ferrocene 1 part, poly (hexamethylene) 0.1 part, hexamethylene diisocyanate 20 parts, pure water 1 part.
Prepare the method for above-mentioned organic polyurethane foam dressing, can carry out according to the following steps:
1. the common polyether polyhydric alcohol of above-mentioned weight, styrene type grafted polyether polyol, ethylenediamine, pentane, polymethyl siloxane-copolyether, ferrocene, poly (hexamethylene), pure water is taken respectively, in room temperature, stir 50s under the condition of 4000r/min, make mixed liquor;
2. the hexamethylene diisocyanate taking above-mentioned weight joins in the mixed liquor that 1. step prepared, and continue to stir 10s, and be incubated 50 minutes at 40 DEG C, obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, and working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:1.5, and processing power is 20w, and the time is 200s, gets product.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.42 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 6 days.
Embodiment two
The organic polyurethane foam dressing of the present invention, be made up of the raw material of following weight parts proportioning: common polyether polyhydric alcohol 10 parts, acrylonitrile type grafted polyether polyol 40 parts, ethylenediamine 17 parts, dichloromethane 3 parts, low-molecular-weight alkoxyl dimethyl polysiloxane 2.5 parts, stannous 2-ethylhexoate 2.5 parts, triclosan 0.4 part, 4,4 '-'-diphenylmethane diisocyanate 50 parts, pure water 2 parts.
Prepare the method for above-mentioned organic polyurethane foam dressing, can carry out according to the following steps:
1. the common polyether polyhydric alcohol of above-mentioned weight, acrylonitrile type grafted polyether polyol, ethylenediamine, dichloromethane, low-molecular-weight alkoxyl dimethyl polysiloxane, stannous 2-ethylhexoate, triclosan and pure water is taken respectively, in room temperature, stir 55s under the condition of 4000r/min, make mixed liquor;
2. take 4 of above-mentioned weight, 4 '-'-diphenylmethane diisocyanate joins in the mixed liquor that 1. step prepared, and continues to stir 15s, and be incubated 40 minutes at 45 DEG C, and obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, and working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:2.5, and processing power is 500w, and the time is 120s, gets product.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.02 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 4 days.
Embodiment three
The organic polyurethane foam dressing of the present invention, is made up of the raw material of following weight parts proportioning: common polyether polyhydric alcohol 7.5 parts, acrylonitrile type grafted polyether polyol 52.5 parts, ethylenediamine 20 parts, isceon 4 parts, low-molecular-weight high alkyl-modified dimethyl polysiloxane 5 parts, triethylene diamine 5 parts, chlorhexidine gluconate 0.8 part, toluene di-isocyanate(TDI) 100 parts, pure water 2 parts.
Prepare the method for above-mentioned organic polyurethane foam dressing, can carry out according to the following steps:
1. the common polyether polyhydric alcohol of above-mentioned weight, acrylonitrile type grafted polyether polyol, ethylenediamine, isceon, low-molecular-weight high alkyl-modified dimethyl polysiloxane, triethylene diamine, chlorhexidine gluconate and pure water is taken respectively, in room temperature, stir 60s under the condition of 4000r/min, make mixed liquor;
2. the toluene di-isocyanate(TDI) taking above-mentioned weight joins in the mixed liquor that 1. step prepared, and continue to stir 22s, and be incubated 30 minutes at 50 DEG C, obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, and working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:3.5, and processing power is 1200w, and the time is 55s, gets product.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.15 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 5 days.
Embodiment four
The organic polyurethane foam dressing of the present invention, be made up of the raw material of following weight parts proportioning: common polyether polyhydric alcohol 15 parts, methyl methacrylate type grafted polyether polyol 30 parts, ethylenediamine 16 parts, hexane 2.5 parts, low-molecular-weight high alkyl-modified dimethyl polysiloxane 3 parts, 1,8-3 parts, diazabicylo 11 carbon-7-alkene, poly (hexamethylene) 0.5 part, hexamethylene diisocyanate 120 parts, pure water 2.5 parts.
Prepare the method for above-mentioned organic polyurethane foam dressing, can carry out according to the following steps:
1. the common polyether polyhydric alcohol of above-mentioned weight, methyl methacrylate type grafted polyether polyol, ethylenediamine, hexane, the high alkyl-modified dimethyl polysiloxane, 1 of low-molecular-weight is taken respectively, 8-diazabicylo 11 carbon-7-alkene, poly (hexamethylene), pure water, in room temperature, stir 52s under the condition of 4000r/min, make mixed liquor;
2. the hexamethylene diisocyanate taking above-mentioned weight joins in the mixed liquor that 1. step prepared, and continue to stir 25s, and be incubated 45 minutes at 42 DEG C, obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, and working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:4.5, and processing power is 1500w, and the time is 30s, gets product.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.57 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 7 days.
Embodiment five
The organic polyurethane foam dressing of the present invention, be made up of the raw material of following weight parts proportioning: common polyether polyhydric alcohol 5 parts, methyl methacrylate type grafted polyether polyol 50 parts, ethylenediamine 18 parts, hexane 3 parts, low-molecular-weight dimethyl polysiloxane 4 parts, stannous 2-ethylhexoate 4 parts, chitosan 1.0 parts, Isosorbide-5-Nitrae-cyclohexane diisocyanate 150 parts, pure water 3 parts.
Prepare the method for above-mentioned organic polyurethane foam dressing, can carry out according to the following steps:
1. the common polyether polyhydric alcohol of following weight, methyl methacrylate type grafted polyether polyol, ethylenediamine, hexane, low-molecular-weight dimethyl polysiloxane, stannous 2-ethylhexoate, chitosan, pure water is taken respectively, in room temperature, stir 55s under the condition of 4000r/min, make mixed liquor;
2. Isosorbide-5-Nitrae-the cyclohexane diisocyanate taking above-mentioned weight joins in the mixed liquor that 1. step prepared, and continue to stir 30s, and be incubated 40 minutes at 45 DEG C, obtained polyurethane foam, is placed in 60 DEG C of vacuum desiccator inner dryings 40 hours, stand-by;
3. polyurethane foam step 2. prepared carries out plasma surface modification process through low temperature plasma generating device, and working gas is the mist of argon and hydrogen, and mixing mol ratio is 1:6, and processing power is 2000w, and the time is 10s, gets product.
Carry out measuring to the drug release rate of the organic polyurethane foam dressing of gained, result shows, through Ar/H
2the medicine speed of disengaging of the organic polyurethane foam dressing of Cement Composite Treated by Plasma gained is 1.27 × 10
-2μ g/cm
2s, and the bacillus pyocyaneus, escherichia coli, staphylococcus aureus, Candida albicans etc. that all can kill dressing interface, prevent foreign body rejection, its effective antibacterial cycle can maintain more than 5 days.