Background technology
Learn from the existing military medicine information of grasping, the former Soviet Union since the eighties just medical activated carbon fiber (ACF) Study on Technology, be listed as military secrecy and carry out clinical trial for surplus in the of 10 years at each military hospital of the former Soviet Union and FAMB.Russia formally is used for the military medicine field at present, mainly this technology is applied to equip the big battlefield of field army and Chem-warrior and each, military hospital, and technology holds in close confidence.Activated carbon fiber has been carried out research constantly both at home and abroad subsequently.But activated carbon fiber of the prior art all has many technical problems such as adsorption capacity is low, poor processability, is not easy to carrying medicament and medical clinical use.
Burn and scald is not only the skin burn, usually is the large tracts of land burn and scald, and general reaction is very strong.Because " barrier " of health puts to rout all along the line and makes blood plasma body fluid (comprising various nutritional labelings, power and water Xie Zhi etc.) exosmose rapidly, cause blood to concentrate and water, electrolyte get muddled, so cause shock, renal function is impaired so that the generation renal function dies of exhaustion dies.
The suppurative infection of pain, the surface of a wound; The infection diffusion of whole body; Scabbing behind the unreasonable intensification that causes the surface of a wound of treatment and the wound healing is the four problems in domestic and international burn and scald field.The surface of a wound has an intense pain and makes patient lie awake all night, have no appetite for food.Usually have to oral or the injection anodyne comes respite pain, but be faced with the side effect of pain relieving narcotics and the danger of infection.In addition, invasive systemic infection is the serious often burn and scald patient successful rescue whether key of control of wound sepsis and septicemia.In the last thirty years, burn and scald infects the first place that always occupies the burn and scald cause of death.After burn takes place, bacterium breeds growth on burn surface of a wound slough, enlarge rapidly and invade to the deep, trauma surface infestation is serious, moist, sepage, blutpunkte and necrotic plaque occur, and then bacteria attack health tissues to the eschar, concentrate on around the blood vessel, even invade in the blood vessel, this moment, the general infection symptom was remarkable, burn wound sepsis promptly takes place, and is further development of septicemia when serious.According to statistics, the septicemia death rate 35.3% occupies dead the first.Wound infection is suppurated, then with local antibacterial medicine and the antibiotic effect of whole body, sterilization, antibacterial in, delayed the healing of the surface of a wound, also make whole body multiplying of some immunocompromised and drug-resistant bacteria occur, the surface of a wound because dry incrustation has temporarily suppressed bacterium, but makes the damage of the surface of a wound continue to deepen in treatment, and the healing of the burn surface of a wound has been increased by one fen obstacle.Because mostly with surgery skin-grafting technology wound closure, so the scar healing is inevitable, and scar tissue itch, pain tempestuously around the clock extremely torment the burn patient to above traditional therapy to degree of depth burn.
Existing treatment burn and scald medicine can not work well, this be since the carrier in these drug products well load treatment burn and scald active pharmaceutical ingredient need the frequent drug products of changing, influenced the healing of the surface of a wound.Therefore, be starved of improved treatment burn and scald medicine carrier and drug products prepared therefrom.
The inventor has studied the influence of activating process (activation temperature, time, atmosphere and catalyst) to activated carbon fiber structure and performance (intensity, pore structure and absorption property); The relation of activated carbon fiber surface chemical structure and pore structure and fester, tissue fluid absorption property; The method of enhanced activity charcoal fiber hydrophily and biocompatibility; The balancing of activated carbon fiber medicament slow release and fester absorption and the method and the concentration of medicine Immesion active carbon fiber.Thereby solved prior art problems.
Technology contents
[problem that will solve]
Therefore, an object of the present invention is to provide a kind of activated carbon fiber that has than strong selectivity adsorption function (target absorption).Simultaneously, with the carrier of this activated carbon fiber, the adsorption function of activated carbon fiber and the treatment function of medicine are effectively combined, thereby reach optimum therapeuticing effect as burn and scald and trauma care medicine.
Another object of the present invention provides the preparation method of this compound activated carbon fiber.
A further object of the present invention provides the drug products of treatment burn and scald and wound.
[technical scheme]
Activated carbon fiber of the present invention has following parameters:
1, the C in the activated carbon fiber, H, O and N content directly determine the functional effect of product, its content (accounting for the percentage of product weight) is respectively 〉=94 ,≤2.5 ,≤2.5 ,≤2.5, C, H, O and N percentage composition reach 98,0.9,0.9,0.2 for best in the actual production.
2, in the prior art, on the one hand, specific area is big more, and adsorption function is strong more; On the other hand, specific area is big more, and activated carbon fiber is crisp more, and product is used difficult more.Yet the specific area of activated carbon fiber of the present invention is 1000-1500m
2/ g, in this scope, activated carbon fiber has low fragility.The optimum of clinical testing is 1100m
2About/g.
3, the size of iodine sorption value and specific area have direct relation (direct proportion).Suitable iodine sorption value 〉=900mg/g, the optimum of clinical testing is about 1100mg/g.
4, pore volume has determined adsorption range, is greater than 0.45cc/g the most substantially,, optimum value is 0.55-0.85cc/g.
5, pore structure and surface chemical structure and fester, tissue fluid adsorptivity have direct and most important relation.
The preparation method of activated carbon fiber of the present invention is as follows:
1, raw-material selection as the raw material of production activated carbon fiber of the present invention, can be used any viscose glue base fiber, and promptly natural fiber material comprises gauze, absorbent cotton, cotton etc.Advantage nontoxic, non-stimulated, no sensitization that these materials have.It is the medical field first-selection.Secondly consider to make raw material with polyacrylonitrile.
2, preparation process, with fibrous material washing and impregnated catalyst, dry then and pre-oxidation (air dielectric, 180-300 ℃, 20-900 minute) and obtain pre-oxygen silk; Pre-oxygen silk is carried out charing (inert gas shielding, 850-1600 ℃ continuously carbonizing 20-900 minute) form the charcoal fiber, activated (activation of 800-1000 ℃ of aqueous vapor) obtains activated carbon fiber; (, promptly control the amount (1-100Nm of steam when activating by the control hole structure again by control activating velocity and soak time
3/ h) (please note: m
3/ h is the unit of the amount of steam, and N is illustrated in the steam under the nitrogen protection, and the general literary style in this field is: Nm
3/ h) and soak time (10-900 minute) prepare needed hole.Pore size is directly proportional with activating velocity and soak time) and carry out surface modification (by the anode electrolysis oxidizing process, also be electrochemical oxidation process: carbon fiber is an anode, graphite cake is a negative electrode, make electrolyte or adopt the mixed method of acid back alkali earlier with acid or alkali, make oxo-anions generate different functional groups, reach the surface modification purpose in the carbon fiber surface discharge) to make activated carbon fiber of the present invention.
In the preparation process, washing is fully washed 30min and is used hollow polyethylene membrane filtration with 40-100 ℃ hot water or boiling water; Impregnated catalyst is CuO (pre-oxidation catalyst), ZnCl
2Solution (carbonization-activation catalyst); Pre-oxidation process: air dielectric, 180-300 ℃ continuous 20-900 minute; Charring process: inert gas shielding, 850-1600 ℃ of continuously carbonizing 20-900 minute activation condition is the activation of 800-1000 ℃ of high pressure aqueous vapor.
The activated carbon fiber of the present invention's preparation is suitable for use as the dressing of treatment burn and scald and wound.The drug products that the present invention treats burn and scald and wound comprises active pharmaceutical ingredient and activated carbon fiber of the present invention.Active medicine is carried in the activated carbon fiber.Wherein the amount of contained active medicine is the treatment effective dose, and concrete amount depends on the active medicine of concrete use usually.Described active medicine is all medicines that are used for the treatment of burn and scald and wound, also can be to treatment burn and scald and the favourable nutrient drug of wound.Specifically, can be selected from antibiotic (for example cefalexin, Cefradine, penicillin, tetracycline, amikacin, gentamicin, erythromycin or the like), physiological electrolyte (as physiological saline, potassium chloride), various nutrient drug (for example vitamin A, B, C, D, H, K, amino acid, glucose or the like).
Yet the substantial connection that worked with it of the contained metal ingredient of catalyst in preparation activated carbon fiber process is above standard and can constitutes danger to wound.In general, (weight with drug products is that calculate on the basis to the content of metallic element in the drug products, is weight ratio.The identification of this content is according to the repeatedly clinical selected index of effect contrast) see the following form 1.
The content of each element of table 1 active medicine in drug products
Element | Content (mg/g) |
????Na | ????<5.0 |
????K | ????<2.0 |
????Ag | ????<0.001 |
????Cu | ????<0.03 |
????Zn | ????<0.05 |
????Ca | ????<0.3 |
Drug products of the present invention can be self-adhering-type burn and scald and wound dressing or be non-self-adhering-type burn and scald and wound dressing, can also be combined into first-aid dressing or first-aid dressing with other auxiliary material.
The preparation method of drug products of the present invention is (can be pharmaceutical aqueous solution with the solution of activated carbon fiber pharmaceutical-impregnated of the present invention, but cannot be the solution of the organic solvent of medicine such as ethanol, propylene glycol) with the adsorption activity medicine, dry then and carry out disinfection and obtain drug products of the present invention.Dry and sterilization method is known to those skilled in the art.
[beneficial effect]
The compound activated carbon fiber material of inventor research and development be new, have unlike the prior art physico-chemical parameter and particular performances, be treatment burn and the new very favorable product of wound.It has the intrinsic chemical inertness of raw material of wood-charcoal material, when contacting, can not produce allergy, stimulation even toxic action, thereby have excellent biological compatibility, not cutaneous growth as burn and trauma care the time with human body, reduce surface of a wound scar and form, help the complete recovery of skin.Because having flourishing surface area and micropore, it gives its high selectivity adsorption capacity and adsorption desorption speed, as treatment burn and wound the time, can adsorb a large amount of festers and wound exudate (comprising bacterium), therefore need not to destroy newborn skin as conventional burn and the frequent replacing of wound gauze, having an intense pain when reducing the patient simultaneously owing to the replacing gauze, thereby to patient's advantageous particularly.And activated carbon fiber of the present invention has not only kept high adsorptivity, has also prevented the fragility under this high absorption property, strengthens this drawing abillity and does not need to add hydroscopic high-molecular resin.
The compound activated carbon fiber material of carrying medicament (being drug products of the present invention) is the simple and effective new material and the new technology for the treatment of burn and wound at present.It can prevent the generation of burn and wound septicopyemia and septicemia.Activated carbon fiber of the present invention is the broad spectrum type adsorbent, and the pore-size distribution of broad just is being suitable for micromolecule and macromolecular absorption such as anti-microbial type medicine, fester such as moisture.Therefore, when being used for the treatment of burn and wound, drug products of the present invention not only has good hygroscopic desiccation effect, and can suppress the breeding of bacterium under damp condition, diminish inflammation in a short time, clean wound, the granulation growth is brought back to life, promote the epithelium of wound to form, improve the recovery process, shorten treatment time, improve the lift face function.
Compound activated carbon fiber of the present invention has the surface of the effect activated carbon fiber prosperity that makes medicament slow release and pore volume and medicine and nutritional labeling are adsorbed on wherein in use slowly discharge then, make the pharmaceutical compositions of the treatment burn of wherein load and wound can play the surface of a wound relieve the pain, anti-infective, reduce inflammation and alleviate therapeutic action such as scar; Make the necessary nutrition of human body of load can act directly on the burn surface of a wound, and be organized absorption, for the Regeneration and Repair of burn and wound and wound surface tissue provides nutrient raw material in the part.Drug products of the present invention has guaranteed the relative stability of drug concentration, brings into play good curative effect, reduces repeatedly coated medicament simultaneously and gives the pain that the patient brought.And, along with medicine slowly-releasing progressively, vacate the hole of fiber, orientation absorption (physical absorption and the chemisorbed) ability and the adsorbance of activated carbon fiber are strengthened, guarantee that wound is in local desinfection chamber state.
Drug products of the present invention also has following characteristics: can be made into soft fabrics such as cloth, felt, thin and light, good permeability reduces the physical activity burden; Form local desinfection chamber at wound, reduce infected danger; Simple to operate, be difficult for coming off voluntarily, reduce dressing change frequency, reduce financial burden.
The specific embodiment
Embodiment 1 is activated carbon fiber of raw material and preparation method thereof with the nonwoven fabric felt
Fully wash nonwoven fabric felt 30min with 40-100 ℃ hot water or boiling water, then oxide impregnation copper and zinc chloride catalyst and dry.Under air dielectric, 200 ℃ of conditions, pre-oxidation 100 minutes; Under inert gas shielding, 850 ℃ of continuously carbonizings 100 minutes; In 800 ℃ high-pressure steam environment, activate into activated carbon fiber.(, promptly control amount (about 50Nm of steam when activating by the adjustment hole structure by control activating velocity and soak time
3/ h) and soak time (400 minutes) prepare needed hole.Pore size is directly proportional with activating velocity and soak time) and make its surface modification (by the anode electrolysis oxidizing process, also be electrochemical oxidation process: carbon fiber is an anode, graphite cake is a negative electrode, make electrolyte or adopt the mixed method of acid back alkali earlier with acid or alkali, make oxo-anions generate different functional groups, reach the surface modification purpose in the carbon fiber surface discharge) to make activated carbon fiber of the present invention.Its C, H, O and N percentage composition are respectively 98,0.9,0.9,0.2 after measured; The specific area of activated carbon fiber is 1250m
2/ g; Pore volume is 0.55cc/g.Its pore structure and surface nature are as shown in table 2 below.
The pore structure of table 2 activated carbon fiber and surface nature
Diameter range () | Shared percentage (%) |
????2-6 | ????3.5 |
????6-10 | ????56.14 |
????10-16 | ????15.62 |
????16-20 | ????6.69 |
????20-30 | ????7.82 |
????30-40 | ????4.3 |
????40-50 | ????2.16 |
????50-100 | ????3.27 |
Embodiment 2 is active activated carbon fiber of raw material and preparation method thereof with absorbent cotton
Use the method identical to prepare activated carbon fiber of the present invention and just replace gauze with absorbent cotton with embodiment.Its C, H, O and N percentage composition are respectively 99,0.6,0.2,0.2 after measured; The specific area of activated carbon fiber is 1100m
2/ g; Pore volume is 0.85cc/g.Its pore structure and surface nature are as shown in table 3 below.
The pore structure of table 3 activated carbon fiber and surface nature
Diameter range () | Shared percentage (%) |
????2-6 | ????5.5 |
????6-10 | ????54.14 |
????10-16 | ????14.62 |
????16-20 | ????7.69 |
????20-30 | ????7.82 |
????30-40 | ????4.3 |
????40-50 | ????2.16 |
????50-100 | ????3.27 |
The tack dressing of embodiment 3 sodium chloride-containing, potassium-potassium chloride drug and activated carbon fiber of the present invention
Component | Weight (gram) |
Hydrophilic active charcoal fiber | ????1000 |
Sodium chloride | ????4 |
Potassium chloride | ????1.4 |
The preparation method: measure in accordance with regulations hydrophilic active charcoal fiber impregnation physiological saline of the present invention 1 hour, it is bonding that dry back and the nonwoven fabric that is scribbled medical adhesive by lining carry out, and the cutting packing is also carried out the drug products that radiosterilization obtains present embodiment.Pore volume is 0.56cc/g.
Embodiment 4 contains the physiological saline of nutrient drug and the non-tack dressing of activated carbon fiber of the present invention
Component | Weight (gram) |
Hydrophilic active charcoal fiber | ????2000 |
Glucose | ????50 |
Sodium chloride, potassium chloride | ????5.5 |
Preparation method:, dryly also carry out the drug products that radiosterilization obtains present embodiment with hydrophilic active charcoal fiber impregnation G/NS solution of the present invention 1 hour.
Embodiment 5 contains the non-tack dressing of penicillin medicine and activated carbon fiber of the present invention
Component | Weight (gram) |
Hydrophilic active charcoal fiber | ????1000 |
Penicillin | ????60 |
Sodium chloride, potassium chloride | ????5.5 |
The preparation method: measure the physiological saline 1 hour that hydrophilic active charcoal fiber impregnation of the present invention is contained penicillin in accordance with regulations, the drug products that radiosterilization obtains present embodiment is also carried out in dry back.Pore volume is 0.56cc/g.
The comparison of embodiment 6 carbon fiber adsorption and catalytic combustion power of the present invention and fragility and prior art:
Prior art: Russian war products specific area is greater than 1500m
2/ g, product is crisp, and hand has been touched bits and has been come off, and needs to be supported by lining during the contact wound.
The present invention: specific area 1000-1500m
2/ g, in this scope, activated carbon fiber has low fragility, and product surface is smooth, and chipless comes off, and can directly act on wound.And the present invention also has the pore volume greater than 0.45cc/g when the surface area of this scope.
The comparison of embodiment 7 drug products slow releasing functions of the present invention and prior art:
Prior art: Russian war products belong to single carbon fiber adsorption and catalytic combustion function, do not have any drug loading, no slow releasing function.
The present invention: attempt first with activated carbon fiber-loaded medicine of the present invention, and carrying medicament and concentration have been selected according to clinical trial result repeatedly, design optimum manufacturing process, reach optimum therapeuticing effect thereby the treatment function of the adsorption function of activated carbon fiber and medicine effectively combined.