CN112281494B - Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing - Google Patents
Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing Download PDFInfo
- Publication number
- CN112281494B CN112281494B CN202011131251.5A CN202011131251A CN112281494B CN 112281494 B CN112281494 B CN 112281494B CN 202011131251 A CN202011131251 A CN 202011131251A CN 112281494 B CN112281494 B CN 112281494B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- polyurethane prepolymer
- hydroxyl
- diisocyanate
- terminated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention relates to a closed polyurethane prepolymer which is soluble in water, and the aqueous solution of the prepolymer is used for post-chemical functionalization of a cotton fabric material, so that the problem of organic volatile matter pollution is solved; secondly, the blocked polyurethane prepolymer does not contain free polyisocyanate, is nontoxic and tasteless, is stable in long-term storage, and is safe and convenient; in addition, the blocked polyurethane prepolymer disclosed by the invention is applied to post-chemical modification of cotton fabric materials, and a blocking agent generated in the thermal deblocking process is adsorbed and retained in the cotton fabric materials, so that the effects of sterilization, antibiosis, disinfection and the like can be achieved. In a word, the blocked polyurethane prepolymer disclosed by the invention is applied to post-chemical function modification of cellulose-based dressing, and is a green and environment-friendly multifunctional technology and method.
Description
Technical Field
The invention relates to an application of a blocked polyurethane prepolymer in preparation of cellulose-based functional dressing, in particular to an isocyanate-terminated polyurethane prepolymer prepared by addition reaction of a hydroxyl-terminated polymer and polyisocyanate; then, blocking the isocyanate group of the isocyanate group-terminated polyurethane prepolymer by using a blocking agent to prepare a blocked polyurethane prepolymer; the closed polyurethane prepolymer is used for preparing cellulose-based medical dressing with the functions of hydrophily, water absorption, moisture retention, moisture permeability, sterilization, antibiosis, bacterium resistance, hemostasis and wound healing promotion, and belongs to the field of medical functional polymer materials.
Background
Cellulose-based medical absorbent cotton, gauze, bandage or cotton pad is widely used in treating scalds, burns and open wounds as a material with wide source, simple production process and low cost. The wound dressing can cover the surface of injured skin or tissue, absorb wound exudate, and provide a microenvironment for protecting and warming the wound and preventing the wound from being infected by external viruses and bacteria. However, the natural cotton dressing has poor moisture absorption and moisture retention performances, is very easy to scab and adhere to skin and muscle, causes secondary injury to wounds, and does not have the sterilization and antibacterial functions. Therefore, in order to obtain a high-performance cellulose-based medical dressing which has balanced moisture absorption, moisture retention and moisture permeability, has the functions of sterilization, antibiosis, bacterium resistance, wound infection prevention, hemostasis, pain relief, wound healing promotion, no adhesion of skin and meat and no secondary injury of dressing change, people begin to perform functional or modified treatment on the cellulose-based dressing from the middle of the last century.
Post-functionalization technologies of cellulose-based dressings mainly include physical loading or mixing, or chemical modification and grafting methods. The cellulose-based dressing disclosed therein is impregnated with Ag+The antibacterial and bactericidal cellulose-based dressing is prepared from triclosan, sulfadiazine, ciprofloxacin, cephalosporin and other medicaments, or chitosan, sodium alginate, cyclodextrin or quaternary ammonium salt and the like are used as functional materials mixed with the cellulose-based dressing. However, the problems of stable drug release, lasting drug effect and the like of the cellulose-based dressing are always problems that people cannot release the drug.
The cellulose-based dressing is composed of cellulose with high crystallinity, a large number of hydroxyl groups are contained on a cellulose macromolecular chain, esterification or etherification reaction can be carried out, or grafting is carried out to carry out structural modification on the cellulose macromolecular chain, and special groups are introduced to ensure that the cellulose-based dressing has different physical, chemical and biological functions, so that the cellulose-based dressing is a hotspot for related cellulose-based dressing functionalization in recent years. For example, CN201210005546.7, CN201510167942.3, CN02134447.7, CN201711029809.7 and CN106146855 utilize the reaction of hydroxyl-terminated polyester and polyisocyanate to prepare isocyanate-terminated prepolymer, and graft with cellulose and its derivatives in organic solvent or ionic liquid to prepare polyester-grafted cellulose, which improves the insolubility of cellulose and enhances the biodegradability of polyester.
CN201580001140.3 provides a reactive antibacterial compound, which is prepared by reacting polyisocyanate with hydroxyethyl tertiary amine, and then performing quaternization reaction on carbamate derivative containing terminal isocyanate group and tertiary amine group, so as to obtain carbamate derivative containing both quaternary ammonium cation or zwitterion group and isocyanate group. And the carbamate derivative containing both quaternary ammonium cation or zwitterion group and isocyanate group is used for treating the durable antibacterial antifouling cotton textile in CN 201580001138.6.
In order to realize the functional modification of the isocyanate-terminated polyurethane prepolymer to polyurethane foam, CN109320680A discloses a multifunctional polyurethane prepolymer and a preparation method thereof, wherein the multifunctional prepolymer containing a polyethylene glycol chain, a quaternary ammonium cation and a salicylaldehyde unit in a molecular structure is prepared by taking polyisocyanate, hydroxyl-terminated polyether tertiary amine and 5-chloromethyl salicylaldehyde as raw materials, and can also be used for post-chemical surface functionalization of the surface of cotton fabric to generate lasting hydrophilic, bactericidal and antifouling functions.
It is well known to the expert that whether the isocyanate-terminated prepolymer grafted cellulose in CN201210005546.7, CN201510167942.3, CN02134447.7, CN201711029809.7 and CN106146855 or the functional isocyanate-terminated polyurethane prepolymer in CN109320680A, CN201580001140.3 and CN201580001138.6 are used for functionally modifying cotton fabrics, the used isocyanate-terminated prepolymer is sensitive to moisture in air, is not long-standing under natural conditions and is difficult to industrially store and transport. In addition, the isocyanate-based polyurethane prepolymer must be used in a dissolved organic solvent, which also causes serious organic Volatile (VOC) in the application process.
It is well known to those skilled in the art that polyethylene glycol (PEG) is a class of amphiphilic polymer, which has excellent moisture retention, lubricity, and softness, and can change the structure of biological membranes of various cells to fuse the cells. According to the molecular design principle of organic chemistry, the hydroxyl-terminated polyethylene glycol monoalkyl ether is selected as a cellulose-based dressing functional reagent, the hydroxyl-terminated polyethylene glycol monoalkyl ether is bonded with cellulose hydroxyl in the cellulose-based dressing through a chemical bond, and the polyethylene glycol monoalkyl ether is bonded on the surface of the cellulose-based dressing, so that the characteristics of the cellulose-based dressing, such as flexibility, hydrophilicity, water absorption and moisture retention, lubricity and the like, are enhanced.
Polyvinylpyrrolidone (PVP) is well known to those skilled in the art as an artificially synthesized water-soluble polymer having properties of an aqueous polymer, such as colloid protection, viscosity, and viscosity,
Film-forming, hygroscopic, solubilizing or condensing action, but most particularly its excellent solubility and physiological compatibility. Has no irritation to skin, mucosa, and eye, and has effects in removing toxic substances, stopping bleeding, preventing peritoneal adhesion, and promoting blood sedimentation. According to the molecular design principle of organic chemistry, the hydroxyl-terminated polyvinylpyrrolidone is selected as a cellulose-based dressing functional reagent and is bonded with cellulose hydroxyl in the cellulose-based dressing through a chemical bond, so that the characteristics of the cellulose-based dressing such as hydrophilic lubrication, hemostasis, detoxification, water absorption, moisture retention and the like are enhanced.
The professional is well aware that the preparation of the disinfectant and the antibacterial sterilizing material is widely applied to both the small molecular quaternary ammonium salt and the high molecular quaternary ammonium salt. According to the molecular design principle of organic chemistry, the hydroxyl-terminated polyether quaternary ammonium salt is selected as a cellulose-based dressing functional reagent and is bonded with cellulose hydroxyl in the cellulose-based dressing through a chemical bond, so that the characteristics of the cellulose-based dressing such as antibiosis, sterilization, hydrophilicity, water absorption and the like are enhanced.
Based on different characteristics and functions of polyethylene glycol, polyvinylpyrrolidone and hydroxyl-terminated polyether quaternary ammonium salt, the bonding quantity and proportion of the modified cellulose dressing on the surface of the cellulose dressing are optimized, so that the hydrophilic, water-absorbing, water-retaining, moisture-permeable and antibacterial functions on the surface of the cellulose dressing can be realized, and the balance of the moisture-absorbing, moisture-retaining and moisture-permeable performances of the modified cellulose dressing is realized; therefore, when the cellulose-based dressing is used, the cellulose-based dressing can absorb exudates to gradually form a wet and smooth antibacterial hydrogel layer, so that a wet and smooth physiological environment with a barrier and a wound healing promoting function is provided for the wound.
Disclosure of Invention
In order to overcome the defects of the existing cellulose-based medical dressing technology and products, the inventor selects a blocked polyurethane prepolymer as a functional reagent of the cellulose-based medical dressing according to a molecular design principle.
Wherein the blocked polyurethane prepolymer is an isocyanate-terminated polyurethane prepolymer prepared by the addition reaction of a hydroxyl-terminated polymer and polyisocyanate; and then, blocking the isocyanate group of the isocyanate group-terminated polyurethane prepolymer by using a blocking agent to prepare the blocked polyurethane prepolymer.
Wherein the hydroxyl-terminated polymer refers to one or more of hydroxyl-terminated polyethylene glycol mono-alkyl ether, single-hydroxyl-terminated polyvinylpyrrolidone and hydroxyl-terminated polyether quaternary ammonium salt, wherein the alkyl refers to C1～C18A hydrocarbyl group.
The polyisocyanate refers to one of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylxylylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or trimethylhexane diisocyanate, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, 1, 6-hexamethylene diisocyanate trimer, isophorone diisocyanate trimer or pentamethylene diisocyanate trimer.
The blocking agent is represented by a general formula (I):
wherein R in the general formula (1)1、R2And R3Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-Or Br-。
The blocked polyurethane prepolymer disclosed by the invention can be thermally deblocked, and the thermally deblocked polyurethane prepolymer has chemical reaction characteristics similar to CN201580001140.3 or CN 109320680A. However, the blocked polyurethane prepolymer can be dissolved in water, and the aqueous solution of the blocked polyurethane prepolymer is used for carrying out post-chemical functional modification on a cotton fabric material, so that the problem of organic matter volatilization pollution is solved; secondly, the blocked polyurethane prepolymer does not contain free polyisocyanate, is nontoxic and tasteless, is stable in long-term storage, and is safe and convenient; in addition, the blocked polyurethane prepolymer disclosed by the invention is applied to post-chemical modification of cotton fabric materials, and a blocking agent generated in the thermal deblocking process is adsorbed and retained in the cotton fabric materials, so that the effects of sterilization, antibiosis, disinfection and the like can be achieved. In conclusion, the blocked polyurethane prepolymer disclosed by the invention is applied to post-chemical function modification of cellulose-based dressings, and belongs to a green and environment-friendly multifunctional technology and method.
The hydroxyl-terminated polyethylene glycol monoalkyl ether is also called polyethylene glycol monoalkyl ether or monohydroxy polyethylene glycol, and specifically refers to the hydroxyl-terminated polyethylene glycol monoalkyl ether with the mass average molecular weight of 600-6000. Wherein said hydrocarbyl radical is C1～C18One kind of hydrocarbyl.
The professional is well aware that the hydroxyl-terminated polyethylene glycol monoalkyl ether is nontoxic and non-irritant, and has wide application in the field of medicine. The polyethylene glycol chain can absorb water secretion of the wound, and combined with water molecules to form a hydration layer, and the hydration layer exists between the cotton dressing and human tissues to prevent the wound surface from further water loss and scabbing or adhering to the dressing.
The single-ended hydroxyl polyvinylpyrrolidone provided by the invention refers to single-ended hydroxyl polyvinylpyrrolidone with an average molecular weight of 1000-6000. The professional is well aware that the single-end hydroxyl polyvinylpyrrolidone has excellent physiological inertia, does not participate in human metabolism, has excellent biocompatibility, does not cause any stimulation to skin, mucosa, eyes and the like, forms a hydrogel layer after combining water, and has excellent skin and muscle wettability.
The hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (II) or a general formula (III):
wherein R in the general formula (II) or the general formula (III)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of the hydrocarbon radicals, X-Refers to Cl-Or Br-N is a natural number in a range of 2-2000, and the sum of p and q is a natural number in a range of 2-200; the preparation of disinfectants and antibacterial materials is widely applied to both small molecular quaternary ammonium salts and large molecular quaternary ammonium salts. According to the molecular design principle of organic chemistry, quaternary ammonium cation polyether is introduced to a cellulose chain of a cellulose-based dressing to be used as a functional reagent of the cellulose-based dressing, and the cellulose-based dressing can be endowed with characteristics and functions of sterilization, antibiosis, hydrophilicity, water absorption, moisture retention and the like.
The invention provides an application of a blocked polyurethane prepolymer in preparation of cellulose-based functional dressing, which is realized by the following steps:
weighing polyisocyanate and an organic solvent in a reactor, controlling the temperature to be 50-130 ℃, slowly adding a mixture of a hydroxyl-terminated polymer and a catalyst, stirring and reacting for 2-12 hours, detecting that the NCO content in materials in the reactor conforms to a preset value, then adding a mixture of a sealing agent and the organic solvent, continuing heat preservation reaction until no NCO is detected in the materials in the reactor, reducing the temperature of the materials in the reactor to room temperature, adding deionized water, standing and layering to obtain a water phase, namely an aqueous solution of the sealed polyurethane prepolymer; putting the dried cellulose-based medical material into the water solution of the blocked polyurethane prepolymer, taking out after dipping-rolling twice, and sending into an oven; or spraying the closed polyurethane prepolymer aqueous solution on the surface layer of the dried cellulose-based medical material, and then sending the cellulose-based medical material into an oven, controlling the temperature to be 100-130 ℃, and drying for 0.03-3 hours to obtain the cellulose-based functional dressing.
Wherein the polyisocyanate refers to one of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylxylylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or trimethylhexane diisocyanate, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, 1, 6-hexamethylene diisocyanate trimer, isophorone diisocyanate trimer or pentamethylene diisocyanate trimer.
The organic solvent is one or more of triethylamine, tributylamine, p-dimethylaminopyridine, N, N, N ', N' -tetramethylethylenediamine, triethylenediamine, N, N-dimethylpiperazine, N-methylmorpholine, acetone, butanone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decahydronaphthalene, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide.
The hydroxyl-terminated polymer refers to one or more than two of hydroxyl-terminated polyethylene glycol mono alkyl ether, single hydroxyl-terminated polyvinylpyrrolidone or hydroxyl-terminated polyether quaternary ammonium salt.
Wherein the hydroxyl-terminated polyethylene glycol monoalkyl ether is also called polyethylene glycol monoalkyl ether or mono-alkoxy polyethylene glycol, and refers to the hydroxyl-terminated polyethylene glycol monoalkyl ether with the mass average molecular weight of 600-6000, wherein the alkyl refers to C1～C18A hydrocarbyl group.
The single-end hydroxyl polyvinylpyrrolidone refers to single-end hydroxyl polyvinylpyrrolidone with the average molecular weight of 1000-6000.
The hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (II) or a general formula (III):
wherein R in the general formula (II) or the general formula (III)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of the hydrocarbon radicals, X-Refers to Cl-Or Br-N is a natural number in a range of 2-2000, and the sum of p and q is a natural number in a range of 2-200;
the catalyst refers to a compound of organic amine and organic tin.
Wherein the organic amine refers to one of triethylamine, tributylamine, p-dimethylaminopyridine, N, N, N ', N' -tetramethylethylenediamine, triethylenediamine, N, N-dimethylpiperazine or N-methylmorpholine.
The organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dibutyldimaleate, dibutyltin didodecylsulfate or dibutyltin diacetate.
The mass ratio of the organic amine to the organic tin is 0.5-5: 0.5-5.
The mass ratio of the polyisocyanate to the hydroxyl-terminated polymer to the catalyst to the organic solvent is 100/50-5000/0.5-5/1-600.
The blocking agent is represented by a general formula (I):
wherein R in the general formula (1)1、R2And R3Are respectively selected from C1～C18One of the hydrocarbon radicals, X-Selected from Cl-Or Br-。
The dosage of the sealing agent is 0.5-5 times of the mass of the polyisocyanate.
The using amount of the deionized water is 2-20 times of the mass of the polyisocyanate.
The cellulose-based medical material refers to one of medical absorbent cotton balls, medical cotton gauze, medical cotton bandages and medical cotton pads which are subjected to drying treatment.
Wherein the dosage of the cellulose-based medical material is 0.05-5 times of the mass of the closed polyurethane prepolymer aqueous solution.
Detailed Description
The present invention provides a use of blocked polyurethane prepolymer in the preparation of cellulose-based functional dressings, which is illustrated in detail by the following specific examples.
EXAMPLE 1 preparation of functional Cotton gauze-1
100 g of toluene diisocyanate, 300 g of dehydrated xylene, 200 g of hydroxyl-terminated polyethylene glycol monomethyl ether with the average molecular weight of 2000, 200 g of single-terminal hydroxyl polyvinylpyrrolidone with the mass average molecular weight of 2000, 200 g of hydroxyl-terminated polyether quaternary ammonium salt with the average molecular weight of 2000 (see formula (II-1)), 2.5 g of stannous octoate and 6 g of triethylene diamine are weighed into a reactor according to the ratio of NCO/OH molar ratio of 2.08, heating to 50-60 ℃ under the protection of nitrogen, stirring for 2-4 hours, detecting the NCO content to 9.8%, adding a mixture of 150 g of a sealing agent shown as the formula (I-1) and 300 g of triethylamine, heating to 80-90 ℃, continuing to react for 12-14 hours, and reducing the temperature of the materials in the reactor to room temperature, adding 1300 g of deionized water, standing for layering, and separating out a xylene phase to obtain a beige closed polyurethane prepolymer-1 aqueous solution. And soaking 100 g of the closed polyurethane prepolymer-1 aqueous solution and 50 g of absorbent cotton gauze in a culture dish, soaking and rolling twice, taking out and squeezing the absorbent cotton gauze, putting the absorbent cotton gauze into an oven at the temperature of 110-130 ℃ for 30 minutes, taking out and cooling to obtain the functional cotton gauze-1.
Wherein the formulae (I-1) and (II-1) have the following structures:
through determination, the weight of the functional cotton gauze-1 is increased by 8.38 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-1 is 631.6 percent which is 3.03 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze, namely 1, is 487.5 percent, which is 2.38 times of the water retention rate of the original absorbent cotton gauze; the functional cotton gauze-1 is naturally and completely immersed in water for 2 to 3 seconds.
EXAMPLE 2 preparation of functional Cotton gauze-2
According to the method and the operation steps of the embodiment 1, 100 g of the water solution of the blocked polyurethane prepolymer-1 in the embodiment 1 is soaked in 50 g of absorbent cotton gauze in a culture dish, the absorbent cotton gauze is soaked and pressed twice, then the absorbent cotton gauze is taken out and squeezed to be dry, the absorbent cotton gauze is placed in an oven at the temperature of 110-130 ℃ for 30 minutes, the absorbent cotton gauze is taken out and drained, the absorbent cotton gauze is placed in the oven at the temperature of 110-130 ℃ for 30 minutes, and the functional cotton gauze-2 is prepared.
Through determination, the weight of the functional cotton gauze-2 is increased by 13.74 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-2 is 1365.3 percent and is 5.92 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze-2 is 525.6 percent, which is 3.02 times of the water retention rate of the original absorbent cotton gauze; the time for the functional cotton gauze-2 to be naturally and completely immersed in the water is 0 second.
EXAMPLE 3 preparation of functional Cotton gauze-3
According to the method and the operation steps of the example 1, the toluene diisocyanate in the example 1 is changed into the isophorone diisocyanate, and the functional cotton gauze-3 is prepared.
Through determination, the weight of the functional cotton gauze-3 is increased by 8.44 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-3 is 635.6 percent which is 3.11 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze-3 is 488.1 percent, which is 2.66 times of the water retention rate of the original absorbent cotton gauze; the time for the functional cotton gauze-3 to be naturally and completely immersed in the water is 3 seconds.
EXAMPLE 4 preparation of functional Cotton gauze-4
The toluene diisocyanate from example 1 was changed to isophorone diisocyanate according to the procedure and procedure of example 1; 200 g of terminal hydroxyl polyethylene glycol monomethyl ether with the average molecular weight of 2000, 200 g of single-terminal hydroxyl polyvinylpyrrolidone with the mass average molecular weight of 2000, 200 g of terminal hydroxyl polyether quaternary ammonium salt with the average molecular weight of 2000 (see formula (II-1)), "changing into 200 g of terminal hydroxyl polyethylene glycol monomethyl ether with the average molecular weight of 2000 and 400 g of terminal hydroxyl polyether quaternary ammonium salt with the average molecular weight of 2000 (see formula (II-1))," and preparing the functional cotton gauze-4.
Through determination, the weight of the functional cotton gauze-4 is increased by 10.32 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-4 is 821.3 percent and is 4.76 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze-4 is 665.3 percent, which is 4.07 times of the water retention rate of the original absorbent cotton gauze; the time for the functional cotton gauze-4 to be naturally and completely immersed in the water is 0 second.
EXAMPLE 5 preparation of functional Cotton gauze-5
According to the method and operation steps of example 1, the toluene diisocyanate in example 1 is changed to isophorone diisocyanate, 200 g of hydroxyl terminated polyethylene glycol monomethyl ether with an average molecular weight of 2000, 200 g of single-terminal hydroxyl polyvinylpyrrolidone with a mass average molecular weight of 2000, 200 g of hydroxyl terminated polyether quaternary ammonium salt with an average molecular weight of 2000 (see formula (II-1)), "200 g of hydroxyl terminated polyethylene glycol monomethyl ether with an average molecular weight of 2000, 400 g of hydroxyl terminated polyether quaternary ammonium salt with an average molecular weight of 2000 (see formula (III-1))," and functional cotton gauze 5 is prepared.
Wherein formula (III-1) has the structure shown below:
wherein n + m in said formula (III-1) is equal to 20.
Through determination, the weight of the functional cotton gauze-3 is increased by 13.62 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-5 is 680.2 percent and is 3.09 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze-5 is 500.3 percent, which is 2.98 times of the water retention rate of the original absorbent cotton gauze; the time for the functional cotton gauze-5 to be naturally and completely immersed in the water is 0 second.
EXAMPLE 6 preparation of functional Cotton gauze-6
According to the method and the operation steps of the embodiment 1, the toluene diisocyanate in the embodiment 1 is changed into isophorone diisocyanate, 200 g of terminal hydroxyl polyethylene glycol monomethyl ether with the average molecular weight of 2000, 200 g of single-terminal hydroxyl polyvinylpyrrolidone with the mass average molecular weight of 2000, 200 g of terminal hydroxyl polyether quaternary ammonium salt with the average molecular weight of 2000 (see the formula (II-1)), "200 g of terminal hydroxyl polyethylene glycol monomethyl ether with the average molecular weight of 2000, 400 g of terminal hydroxyl polyether quaternary ammonium salt with the average molecular weight of 2000 (see the formula (II-1)),", "100 g of blocked polyurethane prepolymer-1 aqueous solution and a culture dish are immersed into 50 g of absorbent cotton gauze, soaked and pressed twice, taken out and squeezed to dry the absorbent cotton, put into an oven at 110-130 ℃ for 30 minutes, and" taken out to dry the absorbent cotton gauze, and (3) placing the cotton gauze in an oven at the temperature of 110-130 ℃ for 30 minutes to obtain the functional cotton gauze-6.
Wherein formula (III-1) has the structure shown below:
wherein n + m in said formula (III-1) is equal to 20.
Through determination, the weight of the functional cotton gauze-3 is increased by 19.76 g relative to the original absorbent cotton gauze, and the saturated water absorption of the functional cotton gauze-6 is 1580.5 percent and is 6.90 times of the saturated water absorption of the original absorbent cotton gauze; the water retention rate of the functional cotton gauze, namely 6, is 680.7 percent, which is 5.03 times of the water retention rate of the original absorbent cotton gauze; the time for the functional cotton gauze-5 to be naturally and completely immersed in the water is 0 second.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (5)
1. The application of the blocked polyurethane prepolymer in the preparation of the cellulose-based functional dressing is realized by the following steps:
weighing polyisocyanate and an organic solvent in a reactor, controlling the temperature to be 50-130 ℃, slowly adding a mixture of a hydroxyl-terminated polymer and a catalyst, stirring and reacting for 2-12 hours, detecting that the NCO content in materials in the reactor conforms to a preset value, then adding a mixture of a sealing agent and the organic solvent into the reactor, continuing heat preservation reaction until no NCO is detected in the materials in the reactor, reducing the temperature of the materials to room temperature, adding deionized water, standing and layering to obtain a water phase, namely an aqueous solution of the sealed polyurethane prepolymer; putting the dried cellulose-based medical material into the closed polyurethane prepolymer aqueous solution, soaking and rolling for two times, taking out, and sending into an oven; or spraying the closed polyurethane prepolymer aqueous solution on the surface layer of a dried cellulose-based medical material, feeding the cellulose-based medical material into an oven, controlling the temperature to be 100-130 ℃, and drying for 0.03-3 hours to obtain the cellulose-based functional dressing, wherein the closed polyurethane prepolymer aqueous solution is characterized by having a structure shown in a general formula (I):
wherein R in the general formula (1)1、R2And R3Are respectively selected from C1~C18One of the hydrocarbon radicals, X-Selected from Cl-Or Br-；
The using amount of the sealing agent is 0.5-5 times of the mass of the polyisocyanate;
the mass ratio of the polyisocyanate to the hydroxyl-terminated polymer to the catalyst to the organic solvent is 100/50-5000/0.5-5/1-600;
the using amount of the deionized water is 2-20 times of the mass of the polyisocyanate;
the dosage of the cellulose-based medical material is 0.05-5 times of the mass of the closed polyurethane prepolymer aqueous solution;
the hydroxyl-terminated polymer refers to one or more than two of hydroxyl-terminated polyethylene glycol mono-alkyl ether, single-ended hydroxyl polyvinylpyrrolidone or hydroxyl-terminated polyether quaternary ammonium salt;
wherein the hydroxyl-terminated polyethylene glycol monoalkyl ether refers to hydroxyl-terminated polyethylene glycol mono-hydrocarbon with the mass-average molecular weight of 600-6000Alkyl ether, wherein the alkyl group means C1~C18A hydrocarbyl group;
the single-ended hydroxyl polyvinylpyrrolidone refers to single-ended hydroxyl polyvinylpyrrolidone with the average molecular weight of 1000-6000;
the hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (II) or a general formula (III):
wherein R in the general formula (II) or the general formula (III)1、R2And R3Are respectively selected from substituted or unsubstituted C1~C18One of the hydrocarbon radicals, X-Refers to Cl-Or Br-N is a natural number in a range of 2-2000, and the sum of p and q is a natural number in a range of 2-200.
2. Use of a blocked polyurethane prepolymer according to claim 1 for the preparation of a cellulose-based functional dressing, wherein the polyisocyanate is one of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylxylylene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 4-cyclohexyl diisocyanate, 1, 4-butylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 10-decamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, 1, 6-hexamethylene diisocyanate trimer, isophorone diisocyanate trimer or pentamethylene diisocyanate trimer.
3. The use of a blocked polyurethane prepolymer in the preparation of cellulose-based functional dressings as defined in claim 1, wherein the organic solvent is one or more of acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decalin, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
4. The application of the blocked polyurethane prepolymer in the preparation of the cellulose-based functional dressing according to claim 1, wherein the catalyst is a compound of organic amine and organic tin, and the mass ratio of the organic amine to the organic tin is 0.5-5: 0.5-5;
wherein the organic amine refers to one of triethylamine, tributylamine, p-dimethylaminopyridine, N, N, N ', N ' -tetramethylethylenediamine, triethylenediamine, N, N ' -dimethylpiperazine or N-methylmorpholine;
the organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dibutyldimaleate, dibutyltin didodecylsulfate or dibutyltin diacetate.
5. Use of a blocked polyurethane prepolymer in the preparation of a cellulose-based functional dressing according to claim 1, wherein the cellulose-based medical material is one of a dried medical absorbent cotton ball, a medical cotton gauze, a medical cotton bandage and a medical cotton pad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011131251.5A CN112281494B (en) | 2020-10-21 | 2020-10-21 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011131251.5A CN112281494B (en) | 2020-10-21 | 2020-10-21 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112281494A CN112281494A (en) | 2021-01-29 |
| CN112281494B true CN112281494B (en) | 2022-03-11 |
Family
ID=74423912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011131251.5A Active CN112281494B (en) | 2020-10-21 | 2020-10-21 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112281494B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061230B (en) * | 2021-03-25 | 2022-05-06 | 江苏海洋大学 | Self-closed polyurethane prepolymer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0267336A (en) * | 1988-09-01 | 1990-03-07 | Sumitomo Bakelite Co Ltd | Manufacture of highly water-absorbing foamed molded item |
| US5135472A (en) * | 1987-02-09 | 1992-08-04 | United Foam Plastics Corporation | Non-linting composite gauze material |
| CA2243367A1 (en) * | 1997-07-17 | 1999-01-17 | Takaya Sato | Water-absorptive polyurethane fiber and method of producing the same |
| US6291578B1 (en) * | 1999-12-16 | 2001-09-18 | Bayer Corporation | Blocked polyisocyanates containing phenolic groups |
| CN109320680A (en) * | 2018-10-12 | 2019-02-12 | 淮海工学院 | A kind of multifunctional polyurethane prepolymer and preparation method thereof |
| CN109354706A (en) * | 2018-10-12 | 2019-02-19 | 淮海工学院 | A kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified |
| CN109467736A (en) * | 2018-11-05 | 2019-03-15 | 长治学院 | A kind of method of modifying of polyurethane foam |
| CN109568636A (en) * | 2018-12-11 | 2019-04-05 | 长春安旨科技有限公司 | A kind of multifunctional polyurethane foam dressing and preparation method thereof |
| FR3086664A1 (en) * | 2018-10-02 | 2020-04-03 | Ophtalmic Compagnie | HYDROGEL COMPOSITIONS |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006099162A2 (en) * | 2005-03-14 | 2006-09-21 | Georgia Tech Research Corporation | Polymeric salen compounds and methods thereof |
-
2020
- 2020-10-21 CN CN202011131251.5A patent/CN112281494B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135472A (en) * | 1987-02-09 | 1992-08-04 | United Foam Plastics Corporation | Non-linting composite gauze material |
| JPH0267336A (en) * | 1988-09-01 | 1990-03-07 | Sumitomo Bakelite Co Ltd | Manufacture of highly water-absorbing foamed molded item |
| CA2243367A1 (en) * | 1997-07-17 | 1999-01-17 | Takaya Sato | Water-absorptive polyurethane fiber and method of producing the same |
| US6291578B1 (en) * | 1999-12-16 | 2001-09-18 | Bayer Corporation | Blocked polyisocyanates containing phenolic groups |
| FR3086664A1 (en) * | 2018-10-02 | 2020-04-03 | Ophtalmic Compagnie | HYDROGEL COMPOSITIONS |
| CN109320680A (en) * | 2018-10-12 | 2019-02-12 | 淮海工学院 | A kind of multifunctional polyurethane prepolymer and preparation method thereof |
| CN109354706A (en) * | 2018-10-12 | 2019-02-19 | 淮海工学院 | A kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified |
| CN109467736A (en) * | 2018-11-05 | 2019-03-15 | 长治学院 | A kind of method of modifying of polyurethane foam |
| CN109568636A (en) * | 2018-12-11 | 2019-04-05 | 长春安旨科技有限公司 | A kind of multifunctional polyurethane foam dressing and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| The mechanical and physical properties of polyurethane composites based on rice husk and polyethylene glycol;Rozman, HD等;《POLYMER TESTING》;20030930;第22卷(第6期);第617-623页 * |
| 医用聚氨酯的改性及其在生物医学中的应用进展;王强等;《塑料科技》;20100910(第09期);第68-73页 * |
| 新型亲水性聚氨酯敷料表面界面性能的研究;黄忠兵等;《航天医学与医学工程》;20011015(第05期);第43-47页 * |
| 甲壳素/壳聚糖医用敷料研究进展;张步宁等;《化工进展》;20080405(第04期);第51-57页 * |
| 羟基聚乙烯吡咯烷酮的制备及其作亲水链段合成水性聚氨酯的研究;李韦东;《万方数据库》;20190806;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112281494A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6705888B2 (en) | Antibacterial dressing and manufacturing method thereof | |
| EP0371736B1 (en) | Wound covering | |
| Corkhill et al. | Synthetic hydrogels VI. Hydrogel composites as wound dressings and implant materials | |
| US20110086077A1 (en) | Silicone hydrogels for tissue adhesives and tissue dressing applications | |
| WO2013109004A1 (en) | Antimicrobial wound-covering material and method for manufacturing same | |
| US20110200655A1 (en) | Systems and methods that kill infectious agents (bacteria) without the use of a systemic anti-biotic | |
| Ngece et al. | Alginate-gum acacia based sponges as potential wound dressings for exuding and bleeding wounds | |
| Namviriyachote et al. | Polyurethane-biomacromolecule combined foam dressing containing asiaticoside: fabrication, characterization and clinical efficacy for traumatic dermal wound treatment | |
| RU2422133C1 (en) | Hydrophylic gel, method of its obtaining (versions), wound covering and based on it bandage means | |
| CN109432484B (en) | Medical super-hydrophobic antibacterial dressing and preparation method thereof | |
| JP2004532815A (en) | Hydrogel wound dressing, and method of making and using the same | |
| WO1992019194A1 (en) | Wound covering material | |
| CN111574728B (en) | Antibacterial polyurethane hydrogel medical dressing and preparation method thereof | |
| EP2072063A1 (en) | Infection-resistant cellular hydrophilic prepolymer based polyurethane foams, methods for producing the same and use thereof in antiseptic wound dressings | |
| CN109432481A (en) | A kind of polyurethane dressing of hemostatic and antibacterial and preparation method thereof | |
| KR20110114195A (en) | Hydrogel patch mixed inorganic materials for pets, and their process | |
| CN107296975A (en) | A kind of antibacterial anti hemorrhagic based composite dressing for medical use and preparation method thereof | |
| CN115124738B (en) | Double-layer bionic drug-loaded hydrogel and preparation and application thereof | |
| CN112281494B (en) | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing | |
| WO2003097727A1 (en) | Hydrophilic foam compositions having antimicrobial properties | |
| JP2018522701A (en) | Wound care products containing alexidine | |
| CN109331215A (en) | A kind of medical antibacterial sponge and preparation method thereof | |
| CN113648454A (en) | Hydrogel dressing carrying metal-polyphenol functional particles and preparation method and application thereof | |
| Parwani et al. | Gum acacia-PVA hydrogel blends for wound healing | |
| KR100359864B1 (en) | Dressing Having Microporous polyurethane film for Wound Healing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |