CN103992459A - Polyurethane resin material dissoluble in ethanol and preparation method of polyurethane resin material - Google Patents
Polyurethane resin material dissoluble in ethanol and preparation method of polyurethane resin material Download PDFInfo
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- CN103992459A CN103992459A CN201410227821.9A CN201410227821A CN103992459A CN 103992459 A CN103992459 A CN 103992459A CN 201410227821 A CN201410227821 A CN 201410227821A CN 103992459 A CN103992459 A CN 103992459A
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/93—Applications in textiles, fabrics and yarns
Abstract
The invention belongs to the field of high-molecular medical materials, and relates to a polyurethane resin material dissoluble in ethanol and a preparation method of the polyurethane resin material. The material can be applied to skin related medicine products, such as a transdermal patch framework material, a liquid bandage, a burn protective coating and the like, as main high-molecular resin. According to the technical scheme, the preparation method comprises the following steps that firstly, polyether glycol and polyisocyanate are polymerized to form a prepolymer; secondly, the prepolymer is subjected to a chain extension process by using small-molecular glycol, and regulating the molecular weight and the molecular structure to realize the usability of the material; and finally, ending the reaction by using ethanol and distilling to remove solvents from the system to obtain the polyurethane resin material which finally can be dissolved in the ethanol.
Description
Technical field
The present invention relates to a kind of polyurethane resin material that is dissolvable in water ethanol and preparation method thereof, material can be used as main body macromolecule resin and is applied to and relates to skin class pharmaceutical prod, such as transdermal patch framework material, liquid bandage, burn supercoat etc.
Background technology
Skin has protection health, resists invasion, perspire cooling, perception environment and maintain the functions such as cylinder electrolyte balance, has shown the characteristics such as high extension, strong moisture-inhibiting and uniport.In the mankind's social activity, skin directly contacts with extraneous, and damage happens occasionally, and is accompanied by the mankind's development for reparation and the protection of skin injury always.Adopt new concept, novel method, novel material, novel process etc. to carry out more convenient, more effective reparation to injured skin, be the direction that scientific research personnel makes great efforts always.
From the eighties in 20th century, researchist starts to be devoted to the development of liquid bandage.Liquid bandage has good cohesiveness, snappiness and intensity.It can fit tightly with skin, and can local motion, waterproof and moisture-inhibiting, can meet the daily life needs as having a bath, swimming.Meanwhile, liquid bandage has the good transparency, is convenient to observe wound recovery situation.Liquid bandage also have carry convenient, simple to operate, germ resistance is good, nontoxic, without sensitization, without removing the advantages such as secondary damage, stable storing, complete processing are simple, replacing gradually traditional treatment of wounds dressing.
US Patent No. 4987893, US5103812, US6627216B2, a series of patents such as US6512023B1 relate to polydimethylsiloxane liquid polymers coating material, European patent EP 2511355A1 invents a kind of cyanacrylate adhesive of waterproof type, it is polyvinyl alcohol that Chinese patent CN200610012150.X has introduced main component, acrylate, the surgery Auxiliary Liquid Material of glycerol, CN200410031161.3 relates to a kind of liquid bandage and preparation method, it is a kind of surface of a wound protection liquid bandage with water-repellancy of main component and preparation method thereof that CN201010584845.1 introduces a kind of soluble cotton.In addition, researchist successively successfully develops cyanoacrylate, cyanoacetic acid ethylene glycol monoethyl ether, hexamethyldisiloxane, 2, the liquid bandage product of the multiple matrix resin materials such as 2,4-trimethylpentane (octane-iso), acrylate terpolymer.
The performance of liquid bandage depends primarily on the material behavior of matrix resin.The resin material using need to have good intensity, snappiness, sanitation performance etc.Particularly importantly possesses good waterproofing and moisture-penetration performances.Wet wound healing theory thinks that moist environment is beneficial to wound healing, and research shows that 2000-2500gm-2day-1 is optimum material water vapor transmittance use range.Urethane is owing to having good biocompatibility, nontoxicity, can serve as liquid bandage matrix resin materials'use without advantages such as sensitization, performance controllabilitys.。
The object of the invention is to prepare a kind of polyurethane resin material that can be dissolved in ethanol, realize dissolve with ethanol and the wholesomeness of material by screening reaction raw materials kind, by regulating reactant ratio to carry out Molecular Structure Design, thereby obtain good mechanical property, adhesiveproperties and waterproof and moisture permeability.The present invention is devoted to the prepared polyurethane resin material that is dissolvable in water ethanol to be applied to liquid bandage field, and extends to the medical field such as Transdermal absorption.The polyurethane resin material that is dissolvable in water ethanol the present invention relates to, has the following advantages: (1) can be dissolved in ethanol system preferably, and sanitation performance is good.(2) good cohesiveness, snappiness and intensity, can be attached to skin surface preferably, also can provide better protection to fold place, joint.(3) excellent waterproofing and moisture-penetration performances, prevents that damaged part is subject to extraneous bacterium infringement, and provides good moistening recovery environment for damaged skin.(4) nontoxicity, without sensitization, be applicable to traditional rubber-like or other types treatment of wounds dressing allergy sufferers to use.(5) material is transparent, is convenient to observe wound recovery situation in use procedure.(6) stable storing, technique is simple.
Summary of the invention
The present invention, by selecting polyether glycol to improve the dissolve with ethanol of urethane, selects hydrophilic chain extender to improve the wetting ability of material, improves the performances such as the strength of materials, toughness by the composite use of chainextender.
Technical scheme of the present invention is: adopt prepolymer method, prepare performed polymer by polyether glycol and isocyanate reaction, use chainextender to carry out chain extension to performed polymer, use ethanol termination reaction, finally remove system solvent and obtain being dissolvable in water the polyurethane resin material of ethanol by distillation.
The polyurethane resin material of ethanol that prepared by the present invention be dissolvable in water can be used as liquid bandage material of main part, is also applicable to the medical field such as Transdermal absorption simultaneously.
Object of the present invention can be achieved through the following technical solutions:
A polyurethane resin material that is dissolvable in water ethanol, is characterized in that, relative molecular mass, between 10000～20000, adopts poly(propylene oxide) polyvalent alcohol, is polymerized hereinafter to be referred as polyether glycol, polyisocyanates, chainextender and ethanol;
This polyurethane resin material comprises following component and quality percentage composition:
The percentage composition sum of each component is 100% above.
Described isocyanate functionality is 2～3, can adopt isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) and trimerization hexamethylene diisocyanate, wherein preferred IPDI.
Described polyether glycol functionality is 2～3, can adopt Polyoxypropylene diol PPG2000, PPG1000, wherein preferred PPG1000.
Described chainextender includes but not limited to dimethylolpropionic acid (DMBA), BDO (BDO), glycol ether (DEG) etc. and compound thereof, wherein the preferably composite use of DMBA/BDO.Described chainextender functionality is 2～3, and relative molecular weight is 45～500.
Described catalyzer can be selected as organic tin catalyzer (as stannous octoate, dibutyl tin laurate), amines catalyst, alkaline metal salt catalyzer, the sub-tin of preferably octanoic acid.
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, is characterized in that, the method comprises the following steps:
1. get the raw materials ready
Prepare raw material according to following component and content (wt%):
2. prepolymer is synthetic
1) under 110～115 DEG C ,-0.95MPa vacuum condition, by polyether glycol processed 1～3h, be cooled to room temperature; Polyether glycol is mixed with polyisocyanates, under N2 atmosphere protection, synthesize performed polymers in 85 ± 5 DEG C of reaction 3～5h;
2) synthetic prepolymer is cooled to 40～50 DEG C, drips chainextender in 1～3h, be then warming up to gradually 75～85 DEG C and continue to add acetone depending on system viscosity in reaction 3h reaction process, hierarchy of control apparent viscosity is less than 20Pas;
3) add ethanol and catalyzer, mix 0.5～1h, termination reaction; Underpressure distillation at 45～65 DEG C, removes acetone and residual ethanol in system, obtains polyurethane resin material.
Gain effect of the present invention is:
1. the polyurethane resin material of preparation has fabulous dissolve with ethanol, and ethanol can be used as bacteriocidal substance as solvent time, on the basis that ensures the performance of material own, has realized medical sanitary requirement;
2. the polyurethane resin material of preparation has good mechanical property, adhesive property and waterproofing and moisture-penetration performances, is suitable as liquid bandage material of main part and uses;
3. the polyurethane resin material preparation method technique that is dissolvable in water ethanol of preparation is simple, reaction conditions is gentle, repeatable strong, and material stability in storage is strong.
4. the polyurethane resin material that is dissolvable in water ethanol of preparation can dissolve alcohol soluble drug preferably, for the exploitation of Chinese medicine reagent product provides good material support, for useful theory study has been carried out in through engineering approaches and the commercialization of Chinese medicine reagent product from now on.
The polyurethane resin material of ethanol that prepared by the present invention be dissolvable in water, realize the dissolve with ethanol of polyurethane material, mechanical property, adhesive property and the waterproofing and moisture-penetration performances that material is good makes it meet the user demand of liquid bandage product, alcohol-soluble polyurethane resin material can dissolve alcohol soluble drug simultaneously, has widened through engineering approaches and the productization development of Chinese medicine reagent product.
Brief description of the drawings
Fig. 1 is Fourier transform infrared (FT-IR) spectrogram of prepared alcohol-soluble polyurethane resin material;
Fig. 2 is differential calorimetric scanning (DSC) curve of prepared alcohol-soluble polyurethane resin material;
Fig. 3 is thermal weight loss (TG) curve of prepared alcohol-soluble polyurethane resin material;
Fig. 4 is gel permeation chromatography (GPC) analytic curve of prepared alcohol-soluble polyurethane resin material.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, is characterized in that, the method comprises the following steps:
1. get the raw materials ready
Prepare raw material according to following component and content (wt%):
The PPG1000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG1000 after IPDI and processed, under T-9 catalysis, N2 atmosphere protection, react 3h in 80 DEG C.
3. prepolymer chain extension
System temperature is down to 50 DEG C, drips the chainextender BDO/DMBA acetone soln of metering quality, continue reaction 3h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
A kind of polyurethane resin material that is dissolvable in water ethanol that preparation method as described in Example 1 synthesizes, tests its microtexture and use properties, analyzes its microtexture by Fig. 1-Fig. 4, and the impact of microtexture on performance is discussed.
Observed from Fig. 1,2270～2280cm-1 place-NCO characteristic group absorption peak disappears, at 1718cm
-1the characteristic peak of place's carbamate groups occurs, illustrates that reaction has generated carbamate groups, NCO group complete reaction.3329cm
-1place is the characteristic peak that N-H stretching vibration produces, 1115cm
-1place is methylene radical stretching vibration characteristic peak, 1343.5cm
-1methylene radical C-H in-plane bending characteristic peak, 2925.1cm
-1it is the stretching vibration characteristic peak of C-H on saturated carbon atom.From analyzing above, the reactions such as PPG1000, IPDI and BDO, DMBA have generated urethane.In Fig. 2, synthetic alcohol-soluble polyurethane material softer section second-order transition temperature is-89.8 DEG C, it is generally acknowledged, in polyurethane molecular structure, there are soft section and hard section two portions, in this experiment owing to having adopted polyether Glycols PPG1000 as soft section of part, on its molecular chain, have the ether that a large amount of internal cohesive energys are little, polarity is low, make Intermolecular Forces less, the material therefore synthesizing has good flexility.Hard section second-order transition temperature is 27.4 DEG C and 59.7 DEG C, and due to one or more state of aggregation forms that hard section part comprises IPDI, DMBA and BDO, the hard section of second-order transition temperature therefore occurring also exists more than one.In Fig. 3, sample starts 210 DEG C of left and right to decompose, and temperature of initial decomposition higher than the use temperature of medical material, decomposes completely at about 380 DEG C far away, testimonial material has the performances such as fabulous heat-resisting oxytolerant is aging thus, and at room temperature can have longer work-ing life.Fig. 4 is gel permeation chromatography (GPC) analysis, this alcohol-soluble polyurethane molecular weight is 14279, relative molecular mass is at 10000～20000, material can be dissolved in ethanol relatively easily, and this scope molecular weight material has the more suitable mechanical property that meets the use of liquid bandage.
Table 1 is the indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 1 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Light yellow, even |
| 2 | Film forming matter outward appearance | ? | Light yellow transparent, tack-free |
| 3 | Stripping strength | N/mm | 0.41 |
| 4 | Tensile strength | MPa | 6.28 |
| 5 | Elongation rate of tensile failure | ％ | 2280 |
| 6 | Surface drying time | s | 141 |
| 7 | Film formation time | s | 210 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 70 |
| 10 | Apparent viscosity | mpa·s，25℃ | 8000 |
| 11 | Rate of perviousness | g/(m 2·day) | 2025 |
| 12 | Water-intake rate | ％ | 5.49 |
| 13 | Stability in storage | Year | ＞1 |
Embodiment 2:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, is characterized in that, the method comprises the following steps:
1. get the raw materials ready
Prepare raw material according to following component and content (wt%):
The PPG1000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG1000 after IPDI and processed, at T-9 catalysis, N
2under atmosphere protection, react 3h in 80 DEG C.
3. prepolymer chain extension
System temperature is down to 50 DEG C, drips the chainextender BDO/DMBA acetone soln of metering quality, continue reaction 3h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
As described in example 2, the alcohol dissolubility medical polyurethane resin material performance test mode of preparation is identical with example 1.Table 2 is indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 2 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Light yellow, even |
| 2 | Film forming matter outward appearance | ? | Light yellow transparent, tack-free |
| 3 | Stripping strength | N/mm | 0.17 |
| 4 | Tensile strength | MPa | 4.09 |
| 5 | Elongation rate of tensile failure | ％ | 1614 |
| 6 | Surface drying time | s | 140 |
| 7 | Film formation time | s | 214 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 60 |
| 10 | Apparent viscosity | mpa·s，25℃ | 4510 |
| 11 | Rate of perviousness | g/(m 2·day) | 2088 |
| 12 | Water-intake rate | ％ | 6.32 |
| 13 | Stability in storage | Year | ＞1 |
Embodiment 3:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, is characterized in that, the method comprises the following steps:
1. get the raw materials ready
Prepare raw material according to following component and content (wt%):
The PPG1000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG1000 after IPDI and processed, at T-9 catalysis, N
2under atmosphere protection, react 3h in 80 DEG C.
3. prepolymer chain extension
System temperature is down to 50 DEG C, drips the chainextender BDO/DMBA acetone soln of metering quality, continue reaction 3h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
As described in example 3, the alcohol dissolubility medical polyurethane resin material performance test mode of preparation is identical with example 1.Table 3 is indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 3 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Light yellow, even |
| 2 | Film forming matter outward appearance | ? | Light yellow transparent, tack-free |
| 3 | Stripping strength | N/mm | 0.13 |
| 4 | Tensile strength | MPa | 2.27 |
| 5 | Elongation rate of tensile failure | ％ | 514.29 |
| 6 | Surface drying time | s | 141 |
| 7 | Film formation time | s | 210 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 40 |
| 10 | Apparent viscosity | mpa·s，25℃ | 1900 |
| 11 | Rate of perviousness | g/(m 2·day) | 2125 |
| 12 | Water-intake rate | ％ | 8.72 |
| 13 | Stability in storage | Year | ＞1 |
Embodiment 4:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, is characterized in that, the method comprises the following steps:
1. get the raw materials ready
Prepare raw material according to following component and content (wt%):
The PPG1000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG1000 after IPDI and processed, at T-9 catalysis, N
2under atmosphere protection, react 3h in 80 DEG C.
3. prepolymer chain extension
System temperature is down to 50 DEG C, drips the chainextender BDO/DMBA acetone soln of metering quality, continue reaction 3h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
As described in example 4, the alcohol dissolubility medical polyurethane resin material performance test mode of preparation is identical with example 1.Table 4 is indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 4 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Light yellow, even |
| 2 | Film forming matter outward appearance | ? | Light yellow transparent, tack-free |
| 3 | Stripping strength | N/mm | 0.13 |
| 4 | Tensile strength | MPa | 1.25 |
| 5 | Elongation rate of tensile failure | ％ | 154.29 |
| 6 | Surface drying time | s | 145 |
| 7 | Film formation time | s | 216 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 20 |
| 10 | Apparent viscosity | mpa·s，25℃ | 500 |
| 11 | Rate of perviousness | g/(m 2·day) | 2001 |
| 12 | Water-intake rate | ％ | 7.78 |
| 13 | Stability in storage | Year | ＞1 |
Embodiment 5:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, the method comprises the following steps:
1. prepare raw material according to following component and content (wt%):
The PPG2000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG2000 after IPDI and processed, at T-12 catalysis, N
2under atmosphere protection, react 4h in 85 DEG C.
3. prepolymer chain extension
System temperature is down to 40～50 DEG C, drips chainextender BDO, continue reaction 2h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
As described in example 5, the alcohol dissolubility medical polyurethane resin material performance test mode of preparation is identical with example 1.Table 5 is indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 5 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Colourless, even |
| 2 | Film forming matter outward appearance | ? | Water white transparency, tack-free |
| 3 | Stripping strength | N/mm | 0.22 |
| 4 | Tensile strength | MPa | 3.39 |
| 5 | Elongation rate of tensile failure | ％ | 407.5 |
| 6 | Surface drying time | s | 142 |
| 7 | Film formation time | s | 214 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 75 |
| 10 | Apparent viscosity | mpa·s，25℃ | 6900 |
| 11 | Rate of perviousness | g/(m 2·day) | 2010 |
| 12 | Water-intake rate | ％ | 5.73 |
| 13 | Stability in storage | Year | ＞1 |
Embodiment 6:
A preparation method who is dissolvable in water the polyurethane resin material of ethanol, the method comprises the following steps:
1. prepare raw material according to following component and content (wt%):
The PPG1000 the using 1.5h that need dewater under 110 DEG C ,-0.95MPa vacuum condition processes.
2. prepolymer is synthetic
In the there-necked flask that condensation reflux unit, temperature control unit, electric mixer are housed, add the PPG1000 after TDI and processed, at T-12 catalysis, N
2under atmosphere protection, react 3h in 85 DEG C.
3. prepolymer chain extension
System temperature is down to 40 DEG C, drips the chainextender BDO/DMBA acetone soln of metering quality, continue reaction 3h after being added dropwise to complete at 75 DEG C of temperature, in reaction process, add acetone depending on system viscosity, hierarchy of control apparent viscosity is less than 20Pas.
4. termination reaction
To adding metering quality ethanol termination reaction in system, acetone and residual ethanol in system are removed in underpressure distillation at 48 DEG C, obtain alcohol-soluble polyurethane resin material.
As described in example 6, the alcohol dissolubility medical polyurethane resin material performance test mode of preparation is identical with example 1.Table 6 is indices of prepared other use propertieies of alcohol-soluble polyurethane resin material.
Table 6 alcohol-soluble polyurethane resin material use properties indices
| ? | Project | Unit | Performance index |
| 1 | Alcoholic solution outward appearance | ? | Yellow, even |
| 2 | Film forming matter outward appearance | ? | Yellow transparent, tack-free |
| 3 | Stripping strength | N/mm | 0.46 |
| 4 | Tensile strength | MPa | 5.39 |
| 5 | Elongation rate of tensile failure | ％ | 407.5 |
| 6 | Surface drying time | s | 142 |
| 7 | Film formation time | s | 212 |
| 8 | Solubleness | G/100g ethanol, 25 DEG C | Approximate 100 |
| 9 | Solid content | ％ | 75 |
| 10 | Apparent viscosity | mpa·s，25℃ | 7000 |
| 11 | Rate of perviousness | g/(m 2·day) | 2056 |
| 12 | Water-intake rate | ％ | 7.23 |
| 13 | Stability in storage | Year | ＞1 |
Claims (8)
1. a polyurethane resin material that is dissolvable in water ethanol, is characterized in that, relative molecular mass, between 10000～20000, adopts poly(propylene oxide) polyvalent alcohol, is polymerized hereinafter to be referred as polyether glycol, polyisocyanates, chainextender and ethanol;
This polyurethane resin material comprises following component and quality percentage composition:
The percentage composition sum of each component is 100% above.
2. a kind of polyurethane resin material that is dissolvable in water ethanol as claimed in claim 1, is characterized in that, described polyether glycol functionality is 2～3, is Polyoxypropylene diol PPG2000 or PPG1000.
3. a kind of polyurethane resin material that is dissolvable in water ethanol as claimed in claim 1, is characterized in that, described polyisocyanates functionality is 2～3.
4. a kind of polyurethane resin material that is dissolvable in water ethanol as claimed in claim 1, is characterized in that, described polyisocyanates is isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate or trimerization tolylene diisocyanate.
5. a kind of polyurethane resin material that is dissolvable in water ethanol as claimed in claim 1, is characterized in that, described chainextender functionality is 2～3, and relative molecular weight is 45～500.
6. a kind of polyurethane resin material that is dissolvable in water ethanol as claimed in claim 1, is characterized in that, described chainextender is BDO BDO, dimethylolpropionic acid DMBA, glycol ether DEG or its composite mixture.
7. a preparation method for the polyurethane resin material that is dissolvable in water ethanol according to claim 1, is characterized in that, this preparation method comprises the following steps:
1) under 110～115 DEG C ,-0.95MPa vacuum condition, by polyether glycol processed 1～3h, be cooled to room temperature; Polyether glycol is mixed with polyisocyanates, under N2 atmosphere protection, synthesize performed polymers in 85 ± 5 DEG C of reaction 3～5h;
2) synthetic prepolymer is cooled to 40～50 DEG C, drips chainextender in 1～3h, be then warming up to gradually 75～85 DEG C and continue to add acetone depending on system viscosity in reaction 3h reaction process, hierarchy of control apparent viscosity is less than 20Pas;
3) add ethanol and catalyzer, mix 0.5～1h, termination reaction; Underpressure distillation at 45～65 DEG C, removes acetone and residual ethanol in system, obtains polyurethane resin material.
8. preparation method as claimed in claim 7, is characterized in that, described catalyzer is organic tin catalyzer, amines catalyst or basic metal salt catalyzer.
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| CN201410227821.9A CN103992459A (en) | 2014-05-26 | 2014-05-26 | Polyurethane resin material dissoluble in ethanol and preparation method of polyurethane resin material |
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| CN112979911A (en) * | 2021-02-03 | 2021-06-18 | 合肥科天水性科技有限责任公司 | Fluorinated polyurethane, shell atomized spray liquid, artificial bionic skin and preparation method |
| CN113679879A (en) * | 2021-08-20 | 2021-11-23 | 广东粤港澳大湾区黄埔材料研究院 | Liquid skin and preparation method and application thereof |
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