CN112029065B - Medical hydrophilic polyurethane sponge and preparation method thereof - Google Patents

Medical hydrophilic polyurethane sponge and preparation method thereof Download PDF

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CN112029065B
CN112029065B CN202010944397.5A CN202010944397A CN112029065B CN 112029065 B CN112029065 B CN 112029065B CN 202010944397 A CN202010944397 A CN 202010944397A CN 112029065 B CN112029065 B CN 112029065B
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polyurethane sponge
hydrophilic polyurethane
water
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CN112029065A (en
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姜志国
谢贵堂
张均
姚明
张化哲
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Suqian Jiahe Plastic Metal Products Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0036Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225Polyamines
    • C08G18/3228Polyamines acyclic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/62Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/04Materials for stopping bleeding

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a medical hydrophilic polyurethane sponge and a preparation method thereof. In the invention, the polyurethane sponge is prepared from the following raw materials in parts by weight: 100 parts of polyethylene glycol (PEG, molecular weight 1000), 45-60 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 2-3 parts of water, 1-2 parts of foam stabilizer, 0.1-0.25 part of stannous octoate, 1-0.5 part of 33% triethylene diamine solution (A33) and 20-30 parts of Polyacrylamide (PAM). The preparation method adopts a A, B bi-component mixed foaming method, is simple, has low cost and is easy to produce. The material can absorb water and swell to achieve the aim of stopping bleeding by mechanically compressing the wound surface, and after swelling, the foam holes are plugged to prevent the new tissue from growing in, so that the material has a positive effect on postoperative recovery of patients.

Description

Medical hydrophilic polyurethane sponge and preparation method thereof
Technical Field
The invention relates to a medical hydrophilic polyurethane sponge and a preparation method thereof, belonging to the field of biomedical materials.
Background
The nasal cavity anatomical structure of human is special, the operation space is narrow, nerves and blood vessels are rich, the hemostatic mode after the operation of a patient is mainly mechanical compression hemostasis, hemostatic dressing is needed to be filled in the nasal cavity, and the hemostatic purpose can be achieved only by filling the nasal cavity with a certain degree of pressure, so that serious nasal compression sense, swelling pain sense, ear distress, sleep disorder, dizziness, headache, tear flow and other uncomfortable senses are often caused to the patient, and therefore, the advantages and disadvantages of the filling material have a great relation with the postoperative response and recovery of the patient. Therefore, the selection of a good hemostatic material for filling is very important for reducing postoperative pain and bleeding of patients and promoting wound healing.
The commonly used hemostatic materials currently available in the domestic market are Merocel expanded sponge and NasoPore degradable absorbent expanded hemostatic sponge produced by polygonic BV corporation of the netherlands. The Merocel expansion sponge needs to provide a mode with larger compression force and longer retention time of the filling material, which is not the optimal hemostatic mode; the Merocel expansion sponge needs to be taken out after operation, and the nasal endoscopy and the operation cavity treatment are carried out for a plurality of times, so that the labor intensity of doctors and the bleeding, adhesion and infection opportunities of the operation cavity are increased. According to the invention, the polyethylene glycol and the polyacrylamide are adopted as the raw materials for preparation, so that the polyurethane sponge has hydrophilicity, absorbs water and swells, the purpose of stopping bleeding by mechanically compressing a wound surface is achieved, after swelling, the foam holes are blocked to prevent the growth of new tissues, after a plurality of days of use, the mechanical strength is reduced, the sponge texture is soft and rotten, the cleaning of a surgical cavity is facilitated, and the method has a positive effect on postoperative recovery of a patient. The development of a convenient-to-pack, easy-to-take-out, non-adhesive and low-cost hemostatic sponge has a great market space.
Disclosure of Invention
The invention provides a medical hydrophilic polyurethane sponge and a preparation method thereof. The doctor puts into the patient's nasal cavity with polyurethane hemostatic sponge, later washes with normal saline, and the preparation raw materials adopts polyethylene glycol and polyacrylamide can make polyurethane sponge have hydrophilicity to swell with water, reaches the hemostatic purpose of mechanical compression surface of a wound, prevents that the new tissue from growing into with the cellular shutoff after swelling, and mechanical strength declines after using several days, and the sponge texture is soft rotten, is favorable to clearing up the art chamber, resumes to the patient postoperative has positive effect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: 100 parts of polyethylene glycol (PEG, molecular weight 1000), 45-60 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 2-3 parts of water, 1-2 parts of foam stabilizer, 0.1-0.25 part of stannous octoate, 1-0.5 part of 33% triethylene diamine solution (A33) and 20-30 parts of Polyacrylamide (PAM).
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture. The invention has the advantages that:
according to the invention, the polyethylene glycol and the polyacrylamide are adopted as the preparation raw materials, so that the polyurethane sponge has water solubility, the surface of the sponge swells after meeting water, the foam holes are blocked to prevent new tissues from growing in, the mechanical strength is reduced after a plurality of days of use, the texture of the sponge is soft and rotten, the cleaning of an operation cavity is facilitated, and the polyurethane sponge has a positive effect on postoperative recovery of a patient.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be specifically described with reference to the following specific examples.
Table 1: the proportions of the components added in examples 1-5 and comparative examples 1-2.
Example 1
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 60 parts, PAM 30 parts, water 3 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Example 2
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 45 parts, PAM 30 parts, water 2 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Example 3
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 45 parts, PAM 20 parts, water 2 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Example 4
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 45 parts, PAM 30 parts, water 2 parts, a foam stabilizer 1 part, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Example 5
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 60 parts, PAM 30 parts, water 3 parts, a foam stabilizer 2 parts, stannous octoate 0.1 parts and A330.5 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Comparative example 1
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 45 parts, water 2 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
Comparative example 2
The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: PEG-1000100 parts, HMDI 20 parts, PAM 30 parts, water 2 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts and A331 parts.
The medical hydrophilic polyurethane sponge comprises the following specific implementation steps:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing the raw materials of polyethylene glycol (molecular weight 1000), water, a foam stabilizer, stannous octoate, A33 and polyacrylamide obtained in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
It should be noted that, the above embodiments are not intended to limit the present invention in any way, and all the technical solutions obtained by adopting equivalent substitution or equivalent transformation fall within the protection scope of the present invention.

Claims (3)

1. The medical hydrophilic polyurethane sponge is characterized by being prepared from the following raw materials in parts by weight: 100 parts of polyethylene glycol (PEG-1000) with molecular weight of 1000, 45-60 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 2-3 parts of water, 1-2 parts of foam stabilizer, 0.1-0.25 part of stannous octoate, 1-0.5 part of 33% triethylene diamine solution (A33) and 20-30 parts of Polyacrylamide (PAM).
2. The medical hydrophilic polyurethane sponge according to claim 1, wherein the molecular weight of the polyethylene glycol (PEG-1000) is 100 parts, HMDI 60 parts, PAM 30 parts, water 3 parts, a foam stabilizer 2 parts, stannous octoate 0.25 parts, a33 parts.
3. A method for preparing a medical hydrophilic polyurethane sponge according to any one of claims 1 or 2, comprising the steps of:
a. weighing the components according to the weight proportion;
b. b, fully and uniformly mixing polyethylene glycol (PEG-1000) with the molecular weight of 1000, water, a foam stabilizer, stannous octoate, A33 and polyacrylamide which are taken in the step a for 1h by mechanical stirring to obtain a component A;
c. weighing the raw material 4,4' -dicyclohexylmethane diisocyanate obtained in the step a as a component B;
d. pouring the component A and the component B into a mold, stirring and mixing at high speed, and performing foaming reaction;
e. cooling to room temperature after the foaming reaction is finished, placing the mixture in an oven at 80 ℃ for solidification for 3 hours, taking out the mixture, and trimming the mixture.
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CN113105601A (en) * 2021-04-10 2021-07-13 西南石油大学 Emulsion separation material of ionic polyacrylamide composite polyurethane foam and preparation method thereof
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CN108359074A (en) * 2018-02-26 2018-08-03 武汉纺织大学 A kind of environment-protecting and high elasticity anti-yellowing polyurethane sponge and preparation method thereof

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KR100777908B1 (en) * 2006-12-19 2007-11-28 주식회사 바이오폴 Moisturizing improved polyurethane foam dressing

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Publication number Priority date Publication date Assignee Title
CN107400350A (en) * 2017-06-30 2017-11-28 南京工业大学 A kind of high-hydroscopicity, high-moisture-retention polyurethane foam and preparation method thereof
CN108359074A (en) * 2018-02-26 2018-08-03 武汉纺织大学 A kind of environment-protecting and high elasticity anti-yellowing polyurethane sponge and preparation method thereof

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