CN113480715A - Polyurethane film dressing and preparation method thereof - Google Patents
Polyurethane film dressing and preparation method thereof Download PDFInfo
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- CN113480715A CN113480715A CN202110852266.9A CN202110852266A CN113480715A CN 113480715 A CN113480715 A CN 113480715A CN 202110852266 A CN202110852266 A CN 202110852266A CN 113480715 A CN113480715 A CN 113480715A
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- stirring
- polyurethane composition
- isocyanate
- diisocyanate
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- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 235000019198 oils Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000036632 reaction speed Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 2
- 239000004359 castor oil Substances 0.000 description 8
- 235000019438 castor oil Nutrition 0.000 description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000037311 normal skin Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- A61L15/42—Use of materials characterised by their function or physical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Engineering & Computer Science (AREA)
- Hematology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane film dressing and a preparation method thereof; the dressing composition comprises: 30-70% of polyether polyol, 20-50% of isocyanate, 0.5-1% of chain extender and 5-30% of solvent; the isocyanate is a mixture of at least one of diphenylmethane-4, 4-diisocyanate and diphenylmethane-2, 4-diisocyanate and aliphatic diisocyanate. According to the invention, by utilizing the characteristic that the reaction speed of aromatic isocyanate and aliphatic isocyanate is different from the reaction speed of polyether polyol, excellent polyurethane which is complementary to each other in comprehensive performance is prepared, and a chain extender is introduced at the later stage, so that the ductility of the resin is further improved, and the resin becomes a film-forming material with excellent performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, relates to a polyurethane film dressing and a preparation method thereof, and particularly relates to a polyurethane composition with moderate hardness and excellent extensibility, a preparation method thereof and application of the polyurethane composition as a medical dressing.
Background
The polyurethane film used as dressing is a transparent and elastic semi-permeable film, and the water vapor permeability is higher than that of normal skin, but lower than the liquid exudation rate of wound surface. The polyurethane film can be used for keeping the wound surface moist, and can allow gas to pass through to promote the wound surface to heal; it is widely used for treating burn and wound surface of donor skin area. Among them, polyether polyurethane films are the mainstream of development. The polyether polyurethane has high moisture permeability, hydrophilicity and elongation at break, good hydrolysis resistance and low tensile strength.
The Chinese patent application of CN 111269558A discloses a preparation method of a polyurethane semipermeable membrane with a retention needle fixed dressing surface layer, which comprises the steps of synthesizing an NCO-terminated polyurethane prepolymer by utilizing polyether diol and toluene diisocyanate, reacting-NCO on the structure of the polyurethane prepolymer with-OH on the structure of N-hydroxyethyl acrylamide to generate an amide modified polyurethane prepolymer by taking N-hydroxyethyl acrylamide as a modifier, and preparing the polyurethane semipermeable membrane by matching auxiliary materials; the prepared polyurethane semipermeable membrane has good waterproof and air permeability. However, since this reaction involves pre-polymerization of polyurethane, the resin film has low hardness and high elasticity, and thus has poor flexibility, low elongation at break, and poor adhesion to the skin.
Disclosure of Invention
The invention aims to provide a polyurethane film dressing and a preparation method thereof. According to the invention, by utilizing the characteristic that the reaction speed of aromatic isocyanate and aliphatic isocyanate is different from the reaction speed of polyether polyol, excellent polyurethane which is complementary to each other in comprehensive performance is prepared, and a chain extender is introduced at the later stage, so that the ductility of the resin is further improved, and the resin becomes a film-forming material with excellent performance.
The invention relates to a polyurethane composition, which comprises the following components in percentage by mass:
30 to 70 percent of polyether glycol,
20 to 50 percent of isocyanate,
0.5 to 1 percent of chain extender,
5 to 30 percent of solvent;
the isocyanate is a mixture of at least one of diphenylmethane-4, 4-diisocyanate and diphenylmethane-2, 4-diisocyanate and aliphatic diisocyanate.
In a preferred embodiment of the present invention, the content of the aliphatic diisocyanate in the isocyanate is 10% to 30% by mass. Too low a stiffness makes the polyurethane film too rigid to be brittle, and too high a stiffness makes the polyurethane film too rigid to meet the application requirements.
In a preferred embodiment of the present invention, the polyether polyol is at least one of vegetable oil polyether polyol, polyoxypropylene triol and glycerol polyether polyol.
In a preferred embodiment of the present invention, the chain extender is an aqueous solution of at least one of sodium 1, 2-propanediol-3-sulfonate, dimethylolbutyric acid and dimethylolpropionic acid.
As a preferable scheme of the invention, the solvent is one or more of benzene, toluene, chlorobenzene, nitrobenzene, acetone, diethyl ether, ethyl acetate and dioxane.
The invention also relates to a preparation method of the polyurethane composition, which is characterized by comprising the following steps:
s1, stirring the isocyanate under the oil bath heating condition until the solution is transparent; adding a solvent, and uniformly stirring and mixing until the solution is transparent; the heating temperature of the oil bath is controlled to be 40-50 ℃;
s2, adding polyether polyol, stirring and mixing uniformly, heating to 100-120 ℃ for reaction, and reacting until the NCO content is 4.0% -4.2%;
and S3, cooling to 30-50 ℃, and dropwise adding a chain extender to react until the solution is uniform and transparent.
In the system of the invention, if the isocyanate is added step by step, on one hand, the time of the whole reaction process is greatly increased due to the inconsistent reaction speed of the aromatic isocyanate and the aliphatic isocyanate and the polyether polyol; on the other hand, the aromatic isocyanate is subjected to implosion by adding step by step, so that the subsequent NCO cannot be accurately measured, and the product performance cannot be ensured due to the fact that the reaction end point cannot be judged.
In a preferred embodiment of the present invention, in step S1, the stirring speed is not more than 100 r/min. Specifically, the stirring speed is 80-100 r/min.
In a preferable scheme of the invention, in the step S2, the stirring and mixing time is 25-30 min, and the stirring speed is not more than 100 r/min; the reaction time is 1.5 to 2.5 hours. As a specific example, the stirring speed is 80 to 100 r/min.
In a preferred embodiment of the present invention, the reaction time in step S2 is 2 hours.
In a preferable embodiment of the present invention, in step S3, the stirring speed is controlled within 50r/min when the chain extender is added dropwise, and the addition is completed within 3 minutes; the reaction time is within half an hour. As a specific example, the stirring speed is controlled to be 30-50 r/min when the chain extender is dripped, and the addition is finished within 2-3 min; the reaction time is 25-30 min.
The invention also relates to application of the polyurethane composition in preparation of the medical polyurethane film dressing.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, by utilizing the characteristic that the reaction speed of the aromatic isocyanate and the aliphatic isocyanate is different from that of polyether polyol, the polyurethane resin with moderate hardness and excellent extensibility is prepared by fractional reaction at different temperatures.
2) The chain extender is introduced to chain extend the slow-reacting aliphatic polyurethane in the later reaction stage, so that the extensibility of the resin is greatly improved, and the resin has high resilience, excellent water resistance and excellent wear resistance after being formed into a film.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention provides a medical polyurethane film dressing which comprises the following components in percentage by mass: 40-60% of polyether polyol, 40-50% of isocyanate, 0.5-1% of chain extender and 20-30% of solvent. Wherein the isocyanate is a mixture of at least one of diphenylmethane-4, 4-diisocyanate and diphenylmethane-2, 4-diisocyanate and aliphatic diisocyanate (HDI trimer). The polyether polyol is at least one of vegetable oil polyether polyol, polyoxypropylene triol and glycerol polyether polyol. The chain extender is an aqueous solution prepared from at least one of 1, 2-propylene glycol-3-sodium sulfonate, dimethylolbutyric acid and dimethylolpropionic acid. The solvent is benzene, toluene, chlorobenzene, nitrobenzene, acetone, diethyl ether, ethyl acetate, dioxane.
The preparation method of the medical polyurethane film dressing comprises the following steps:
(1) accurately weighing isocyanate respectively under strict requirements, putting the isocyanate into a heating reaction kettle with an oil bath, and uniformly stirring and mixing until the solution is transparent; the temperature is controlled to be 40-50 ℃, and the stirring speed is not more than 100 r/min.
(2) And (2) adding the solvent which is 30 percent of the mass of the isocyanate in the step (1) into a reaction kettle, and uniformly stirring and mixing until the solution is transparent, wherein the stirring speed is not more than 100 r/min.
(3) Accurately weighing polyether polyol strictly according to theoretical guidance requirements, putting the polyether polyol into a reaction kettle, uniformly stirring and mixing for half an hour, wherein the stirring speed is not more than 100 r/min.
(4) And (3) raising the temperature in the reaction kettle to 100-120 ℃, adding a cooling reflux device, reacting for 2 hours under the condition, titrating the NCO content to reach a theoretical calculated value of 4.0-4.2%, and then carrying out the next reaction.
(5) Controlling the temperature of the reaction kettle at 30-50 ℃, controlling the stirring speed at 50r/min, dropwise adding the chain extender into the reaction kettle, finishing the addition within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
Example 1
The embodiment relates to a polyurethane film dressing and a preparation method thereof; the method comprises the following specific steps:
(1) 85g of diphenylmethane-4, 4-diisocyanate and 15g of aliphatic diisocyanate (HDI trimer) were accurately weighed. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 50 ℃, and the stirring speed is 80 r/min.
(2) Adding 40g of acetone, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 80r/min 1.
(3) 231g of castor oil is accurately weighed and put into a reaction kettle, and the mixture is stirred and mixed evenly for half an hour at the stirring speed of 100 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 30 ℃, controlling the stirring speed at 50r/min, dropwise adding 2g of 75% dimethylolbutyric acid aqueous solution into the reaction kettle within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
Example 2
The embodiment relates to a polyurethane film dressing and a preparation method thereof; the method comprises the following specific steps:
(1) 80g of diphenylmethane-2, 4-diisocyanate and 20g of aliphatic diisocyanate (HDI trimer) were accurately weighed. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 40 ℃, and the stirring speed is 100 r/min.
(2) Adding 45g of diethyl ether, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 100r/min 1.
(3) 350g of polyoxypropylene triol is accurately weighed and put into a reaction kettle, and the mixture is stirred and mixed evenly for 25min at the stirring speed of 80 r/min.
(4) The temperature in the reaction kettle is raised to 120 ℃, a cooling reflux device is added, and after the reaction is carried out for 1.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.0 percent.
(5) And controlling the temperature of the reaction kettle at 50 ℃, controlling the stirring speed at 30r/min, dropwise adding 5g of 75% dimethylolpropionic acid aqueous solution into the reaction kettle within 2 minutes, and reacting for 25min until the solution is uniform and transparent to obtain the required product.
Example 3
The embodiment relates to a polyurethane film dressing and a preparation method thereof; the method comprises the following specific steps:
(1) 70g of diphenylmethane-4, 4-diisocyanate and 30g of aliphatic diisocyanate (HDI trimer) were accurately weighed. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 45 ℃, and the stirring speed is 90 r/min.
(2) Adding 38g of nitrobenzene, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 90r/min 1.
(3) Accurately weighing 60g of glycerol polyether polyol, putting the glycerol polyether polyol into a reaction kettle, and uniformly stirring and mixing the glycerol polyether polyol for 30min at the stirring speed of 90 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 40 ℃, controlling the stirring speed at 40r/min, dropwise adding 2g of 75% dimethylolpropionic acid aqueous solution into the reaction kettle within 3 minutes, and reacting for 30 minutes until the solution is uniform and transparent to obtain the required product.
Example 4
The embodiment relates to a polyurethane film dressing and a preparation method thereof; the method comprises the following specific steps:
(1) 89g of diphenylmethane-4, 4-diisocyanate and 29g of aliphatic diisocyanate (HDI trimer) were accurately weighed. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 50 ℃, and the stirring speed is 85 r/min.
(2) 120g of dioxane is added, the mixture is stirred for 10min and mixed evenly until the solution is clear and transparent, and the stirring speed is 85r/min 1.
(3) 160g of castor oil is accurately weighed and put into a reaction kettle, and the castor oil is uniformly stirred and mixed for half an hour at the stirring speed of 100 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 30 ℃, controlling the stirring speed at 50r/min, dropwise adding 2g of 1, 2-propylene glycol-3-sodium sulfonate 75% aqueous solution into the reaction kettle, completing the addition within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
Comparative example 1
The present comparative example relates to a polyurethane film dressing and a method of making the same; the method comprises the following specific steps:
(1) 100g of diphenylmethane-4, 4-diisocyanate was weighed out accurately. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 50 ℃, and the stirring speed is 80 r/min.
(2) Adding 40g of acetone, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 80r/min 1.
(3) 364g of castor oil is accurately weighed and put into a reaction kettle, and the mixture is stirred and mixed evenly for half an hour at the stirring speed of 100 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 30 ℃, controlling the stirring speed at 50r/min, dropwise adding 2g of 75% dimethylolbutyric acid aqueous solution into the reaction kettle within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
Comparative example 2
The present comparative example relates to a polyurethane film dressing and a method of making the same; the method comprises the following specific steps:
(1) 100g of aliphatic diisocyanate (HDI trimer) was weighed out accurately. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 50 ℃, and the stirring speed is 80 r/min.
(2) Adding 40g of acetone, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 80r/min 1.
(3) Accurately weighing 52g of castor oil, putting the castor oil into a reaction kettle, and uniformly stirring and mixing for half an hour at the stirring speed of 100 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 30 ℃, controlling the stirring speed at 50r/min, dropwise adding 2g of 75% dimethylolbutyric acid aqueous solution into the reaction kettle within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
Comparative example 3
(1) 100g of isophorone diisocyanate (IPDI trimer) is weighed out accurately. Putting into a heating reaction kettle with an oil bath, and stirring for 10min until the uniformly mixed solution is transparent; the temperature is controlled at 50 ℃, and the stirring speed is 80 r/min.
(2) Adding 40g of acetone, stirring for 10min, uniformly mixing until the solution is clear and transparent, and stirring at the speed of 80r/min 1.
(3) Accurately weighing 312.5g of castor oil, putting the castor oil into a reaction kettle, and uniformly stirring and mixing for half an hour at the stirring speed of 100 r/min.
(4) The temperature in the reaction kettle is raised to 110 ℃, a cooling reflux device is added, and after the reaction is carried out for 2.5 hours under the condition, the NCO content is titrated to reach the theoretical calculated value of 4.2%.
(5) And controlling the temperature of the reaction kettle at 30 ℃, controlling the stirring speed at 50r/min, dropwise adding 2g of 75% dimethylolbutyric acid aqueous solution into the reaction kettle within 3 minutes, and reacting for half an hour until the solution is uniform and transparent to obtain the required product.
The resulting resin scratch film was subjected to standard tests according to ASTM-D5034, ASTM D4157, ASTM D737-2018, JIS L1099-2006, and the corresponding physical property data are shown in Table 1 below:
TABLE 1
As can be seen from table 1, the difference between the isocyanate used in example 1 and comparative examples 1 and 2 results in a great difference in the properties of the finally obtained resin films, and only when the aromatic isocyanate and the aliphatic isocyanate are simultaneously reacted, the aromatic polyurethane provides a hard segment, and the aliphatic polyurethane provides a soft segment, the resin films with good ductility, water resistance and wear resistance are finally obtained.
The above is a description of specific examples of the present invention and comparative examples. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various modifications may be made by those skilled in the art within the scope of the appended claims without affecting the true spirit of the invention.
Claims (10)
1. The polyurethane composition is characterized by comprising the following components in percentage by mass:
30 to 70 percent of polyether glycol,
20 to 50 percent of isocyanate,
0.5 to 1 percent of chain extender,
5 to 30 percent of solvent;
the isocyanate is a mixture of at least one of diphenylmethane-4, 4-diisocyanate and diphenylmethane-2, 4-diisocyanate and aliphatic diisocyanate.
2. The polyurethane composition according to claim 1, wherein the aliphatic diisocyanate is contained in the isocyanate in an amount of 10 to 30% by mass.
3. The polyurethane composition of claim 1, wherein the polyether polyol is at least one of a vegetable oil polyether polyol, a polyoxypropylene triol, and a glycerol polyether polyol.
4. The polyurethane composition of claim 1, wherein the chain extender is an aqueous solution of at least one of sodium 1, 2-propanediol-3-sulfonate, dimethylolbutyric acid, dimethylolpropionic acid.
5. The polyurethane composition of claim 1, wherein the solvent is one or more selected from benzene, toluene, chlorobenzene, nitrobenzene, acetone, diethyl ether, ethyl acetate, and dioxane.
6. A method for preparing a polyurethane composition according to claim 1, comprising the steps of:
s1, stirring the isocyanate under the oil bath heating condition until the solution is transparent; adding a solvent, and uniformly stirring and mixing until the solution is transparent; the heating temperature of the oil bath is controlled to be 40-50 ℃;
s2, adding polyether polyol, stirring and mixing uniformly, heating to 100-120 ℃ for reaction, and reacting until the NCO content reaches 4.0% -4.2%;
and S3, cooling to 30-50 ℃, and dropwise adding a chain extender to react until the solution is uniform and transparent.
7. The method of claim 6, wherein the stirring speed is 80 to 100r/min in step S1.
8. The method for preparing the polyurethane composition according to claim 6, wherein in step S2, the stirring and mixing time is 25-30 min, and the stirring speed is 80-100 r/min; the reaction time is 1.5 to 2.5 hours.
9. The method for preparing the polyurethane composition according to claim 6, wherein in step S3, the stirring speed is controlled to be 30-50 r/min when the chain extender is added dropwise, and the addition is completed within 2-3 min; the reaction time is 25-30 min.
10. Use of the polyurethane composition of claim 1 in the preparation of a medical polyurethane film dressing.
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