CN104311781A - High-moisture-permeability aqueous polyurethane material and preparation method thereof - Google Patents
High-moisture-permeability aqueous polyurethane material and preparation method thereof Download PDFInfo
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- CN104311781A CN104311781A CN201410594709.9A CN201410594709A CN104311781A CN 104311781 A CN104311781 A CN 104311781A CN 201410594709 A CN201410594709 A CN 201410594709A CN 104311781 A CN104311781 A CN 104311781A
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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Abstract
The invention aims to provide a high-moisture-permeability aqueous polyurethane material, which has high moisture permeability and is used in the dry-process coating finishing for cotton and dacron textile products, and a preparation method of the aqueous polyurethane material. The high-moisture-permeability aqueous polyurethane material is composed of polyurethane resin and water, wherein the polyurethane resin is prepared from the following components in percentage by weight: 40wt-80wt% of long-chain polyol, 10wt%-50wt% of a diisocyanate compound, 1wt%-10wt% of an anionic hydrophilic compound, 0.05wt%-5wt% of a hydroxyl-containing low molecular compound and 1wt%-5wt% of ethylenediamine; and the weight percentage of the aqueous polyurethane material in water is kept at 50wt%-75wt%. When the aqueous polyurethane material provided by the invention is prepared into a textile coating agent and the textile coating agent is applied to a dacron fabric by adopting the dry-process finishing, the moisture permeable rates of all the obtained fabrics are more than 5000g/m<2>.day.
Description
Technical field
The present invention relates to a kind of high moisture-inhibiting water-base polyurethane material and preparation method thereof, belong to technical field of textile chemical engineering.
Background technology
As far back as the sixties in 20th century, urethane (PU) synthetic leather just starts to appear in the life of people.PU synthetic leather kishke feel is strong, have strong with base material cohesive force, resistance to wear, flex endurant, the excellent properties such as anti-aging, and process easy, cheap.Along with improving constantly of people's living standard, to PU remove from office comfortable features of clothing and functional requirement also more and more higher.Early stage PU coated fabric waterproof effect is general all better, but moisture-inhibiting ability is poor, and human body wears this kind of clothes when strenuous exercise, and a large amount of sweat cannot be discharged as a vapor, forms condensing drip, make people feel sticky wet and uncomfortable in clothes inside.Therefore the research of waterproof moisture-penetrating urethane become the hot subject of urethane research field.Waterproof and breathable (also known as Waterproof Breathable) refers to that polymer materials does not allow the penetration by liquid such as water droplet, but can ensure water vapour freely through.The later stage sixties 20th century, the states such as the U.S., Japan, Belgium started to develop microporous polyurethane coated fabric and Hdyrophilic polyurethane film-fabric, and the research and development of the Waterproof Breathable coating substance after this based on urethane are always very active to the beginning of the seventies.
Although solvent borne polyurethane textile coating agent water vapour permeability is better, because it contains a large amount of organic solvent, the residual isocyanate monomer in serious environment pollution, particularly solvent-type double-component urethane, toxicity is high.Along with enhancing and national governments' environmental protection legislation of people's environmental consciousness, be badly in need of a kind of new polyurethane material that can substitute conventional organic solvents type.Aqueous polyurethane substitutes organic solvent as dispersion medium using water, has safe, inexpensive, energy-conservation, environmental friendliness, the feature such as easy to use, therefore receive much concern, become the important directions of current polyurethane loomage coatings art development.Chinese patent CN102633977A discloses a kind of Waterproof Breathable coating adhesive, preparation method and application thereof, this polyurethane coating agent utilizes prepolymer method with polyether Glycols and vulcabond grafting long-chain saturated fatty alcohol modified synthesis aqueous polyurethane, but its vapor transfer rate is lower.The vapor transfer rate of a kind of high moisture-inhibiting water-base polyurethane material of the present invention's synthesis is generally higher than 5000g/m
2day, and water pressure resistance all can reach waterproof service requirements.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of for the Waterproof Breathable water-base polyurethane material in the top finish of cotton, Polyester Textiles etc. and preparation method, make it meet environmental friendliness, the Waterborne Polyurethane Fabric Coatings of high moisture-inhibiting requirement can be met again.
Technical scheme: the high moisture-inhibiting water-base polyurethane material of one of the present invention is achieved through the following technical solutions:
This material is made up of urethane resin and water, and urethane resin is made up of each component of following weight percent: the long-chain polyols compound of 40wt% ~ 80wt%, 10wt% ~ 50wt% diisocyanate cpd, the anionic hydrophilic compounds of 1wt% ~ 10wt%, the low molecular compound of 0.05wt% ~ 5wt% hydroxyl, the quadrol of 1wt% ~ 5wt%; In the water-base polyurethane material be made up of urethane resin and water, the weight percent of water is 50wt% ~ 75wt%.
The preparation method of high moisture-inhibiting water-base polyurethane material of the present invention is:
Long-chain polyols compound, anionic hydrophilic compounds and the low molecular compound containing hydroxyl are added in reactor simultaneously, at 70 ~ 90 DEG C, stir 0.5 ~ 1h mix to obtain glycol mixed solution, after this glycol mixed solution is cooled to 40 ~ 55 DEG C, add diisocyanate cpd, be warming up to 60 ~ 80 DEG C, reaction 6 ~ 8h, obtains the base polyurethane prepolymer for use as of isocyanate group end-blocking; This performed polymer is cooled to 15 ~ 40 DEG C, and to add with this performed polymer total mass ratio be that the butanone of 0.2:1 ~ 0.3:1 dilutes, the triethylamine that to add with anionic hydrophilic compounds mol ratio be again 0.9:1 ~ 1.1:1 carries out neutralization reaction 0.5 ~ 1h, in obtaining and mixed solution; Under high-speed stirring toward in and in mixed solution, to add with above-mentioned performed polymer total mass ratio be the deionized water of 1:1 ~ 3:1, emulsification 0.5 ~ 1h, then add quadrol and carry out chain extending reaction 0.5 ~ 1h, obtain aqueous polyurethane emulsion; By this aqueous polyurethane emulsion, at 40 ~ 50 DEG C, underpressure distillation is except desolventizing, and the weight percent keeping water in this water-base polyurethane material is 50wt% ~ 75wt%, obtains the high moisture-inhibiting water-base polyurethane material that solid content is 25wt% ~ 50wt%.
The molecular weight that described long-chain polyols compound is 40wt% ~ 80wt% by weight percent to be the polyoxyethylene glycol of 1000 ~ 3000 and the molecular weight of 20wt% ~ 60wt% be 1000 ~ 3000 polytetrahydrofuran diol form.
Described diisocyanate cpd is the one in hydrogenation of benzene dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
Described anionic hydrophilic compounds is the one in dimethylol propionic acid, dimethylolpropionic acid.
The low molecular compound of described hydroxyl is BDO, TriMethylolPropane(TMP), 1,6-hexylene glycol, glycol ether, 3-methyl isophthalic acid, one or more the combination in 5-pentanediol.
Performance test: by high for one of the present invention moisture-inhibiting water-base polyurethane material, add 0.2wt%L75N thickening material and 0.1wt%BYK333 wetting agent obtains Waterborne Polyurethane Fabric Coatings, adopt dry method to arrange on polyester piece good this coating-forming agent, measure water vapour permeability and the water resistance of coated fabric according to " GB/T12704.1-2009 textile fabric water vapour permeability test method part 1: moisture absorption method " and " GB/T4744-1997 textile fabric water permeability resistance measures water pressure resistance test ".
Beneficial effect: the invention provides a kind of high moisture-inhibiting water-base polyurethane material and preparation method thereof, compared with prior art, there is following characteristics:
(1) compared with traditional solvent-borne polyurethane loomage coating-forming agent, the present invention is to provide a kind of take water as the Waterborne Polyurethane Fabric Coatings of dispersion medium, has safe, inexpensive, energy-conservation, environmental friendliness, the feature such as easy to use.
(2) the present invention is by using polyoxyethylene glycol and polytetrahydrofuran diol admixtured polyether diol compound as soft section of urethane, and make the polyurethane material obtained not only have the performance of high moisture-inhibiting by the suitable molecular weight of both selections and ratio, and have that physical strength is good, the feature of excellent hydrolysis resistance, while meeting the basic use properties of basic material, the vapor transfer rate of fabric can be significantly improved.
Embodiment
The molecular weight that long-chain polyols compound described in high moisture-inhibiting water-base polyurethane material of the present invention is 40% ~ 80% by weight percent to be the polyoxyethylene glycol (PEG) of 1000 ~ 3000 and the molecular weight of 20% ~ 60% be 1000 ~ 3000 polytetrahydrofuran diol (PTMG) form; Described vulcabond is the one in hydrogenation of benzene dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI); Described anionic hydrophilic compounds is the one in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA); The low molecular compound of described hydroxyl comprises: 1,4-butyleneglycol (BDO), TriMethylolPropane(TMP) (TMP), 1,6-hexylene glycol (HDO), glycol ether (DEG), 3-methyl isophthalic acid, one or more the combination in 5-pentanediol (MPD).
Embodiment 1:
By 78.18g molecular weight be 2000 polyoxyethylene glycol and 52.12g molecular weight be 2000 polytetrahydrofuran diol, 8g dimethylolpropionic acid, 1.68g glycol ether add in reactor simultaneously, 1h is stirred at 70 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 40 DEG C, add 60g isophorone diisocyanate compound, be warming up to 60 DEG C, reaction 8h, obtains the base polyurethane prepolymer for use as of isocyanate group end-blocking; This performed polymer is cooled to 20 DEG C, add the butanone dilution of 40g, add 5.46g triethylamine again, during neutralization reaction 0.5h obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 205g deionized water, emulsification 0.5h, add 4.87g quadrol again, continue high-speed stirring 0.5h, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 40 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 50%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5000g/m
2day, water pressure resistance are 73.5KPa.
Embodiment 2:
By 55.8g molecular weight be 2000 polyoxyethylene glycol and 77.4g molecular weight be the polytetrahydrofuran diol of 2000, 6g dimethylolpropionic acid, 2.8g TriMethylolPropane(TMP) and 2.57g1, 4-butyleneglycol adds in reactor simultaneously, 0.5h is stirred at 90 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 55 DEG C, add 60g isophorone diisocyanate compound, be warming up to 80 DEG C, reaction 6h, obtain the base polyurethane prepolymer for use as of isocyanate group end-blocking, this performed polymer is cooled to 40 DEG C, add the butanone dilution of 60g, add 4.10g triethylamine again, during neutralization reaction 0.5h obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 600g deionized water, emulsification 0.5h, add 2.78g quadrol again, continue high-speed stirring 0.5h, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 50 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 25%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5100g/m
2day, water pressure resistance are 50.9KPa.
Embodiment 3:
By 69g molecular weight be 3000 polyoxyethylene glycol and 69g molecular weight be the polytetrahydrofuran diol of 1000, 6g dimethylol propionic acid, 5.9g3-methyl isophthalic acid, 5-pentanediol adds in reactor simultaneously, 45min is stirred at 80 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 50 DEG C, add 50g isophorone diisocyanate compound, be warming up to 70 DEG C, reaction 7h, obtain the base polyurethane prepolymer for use as of isocyanate group end-blocking, this performed polymer is cooled to 30 DEG C, add the butanone dilution of 50g, add 4.07g triethylamine again, during neutralization reaction 45min obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 530g deionized water, emulsification 0.5h, add 2.25g quadrol again, continue high-speed stirring 45min, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 50 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 27%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5200g/m
2day, water pressure resistance are 60.4KPa.
Embodiment 4:
By 78.34g molecular weight be 2000 polyoxyethylene glycol and 52.23g molecular weight be the polytetrahydrofuran diol of 1000, 8g dimethylol propionic acid, 1.44g3-methyl isophthalic acid, 5-pentanediol adds in reactor simultaneously, 50min is stirred at 75 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 45 DEG C, add 60g4, 4 '-dicyclohexyl methane diisocyanate compound, be warming up to 65 DEG C, reaction 7.5h, obtain the base polyurethane prepolymer for use as of isocyanate group end-blocking, this performed polymer is cooled to 35 DEG C, add the butanone dilution of 60g, add 5.43g triethylamine again, during neutralization reaction 50min obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 300g deionized water, emulsification 0.5h, add 2.36g quadrol again, continue high-speed stirring 50min, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 45 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 40%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5400g/m
2day, water pressure resistance are 70.6KPa.
Embodiment 5:
By 87.9g molecular weight be 2000 polyoxyethylene glycol and 58.6g molecular weight be the polytetrahydrofuran diol of 2000, 6g dimethylolpropionic acid, 2.43g1, 6-hexylene glycol adds in reactor simultaneously, 1h is stirred at 65 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 50 DEG C, add 45g hexamethylene diisocyanate compound, be warming up to 70 DEG C, reaction 7h, obtain the base polyurethane prepolymer for use as of isocyanate group end-blocking, this performed polymer is cooled to 20 DEG C, add the butanone dilution of 55g, add 4.09g triethylamine again, during neutralization reaction 0.5h obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 466g deionized water, emulsification 0.5h, add 6.44g quadrol again, continue high-speed stirring 1h, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 42 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 30%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5500g/m
2day, water pressure resistance are 74.7KPa.
Embodiment 6:
By 58.2g molecular weight be 2000 polyoxyethylene glycol and 58.2g molecular weight be the polytetrahydrofuran diol of 3000, 8g dimethylolpropionic acid, 2g TriMethylolPropane(TMP), 8.86g glycol ether adds in reactor simultaneously, 50min is stirred at 80 DEG C, mix to obtain glycol mixed solution, this glycol mixed solution is cooled to 50 DEG C, add 65g4, 4 '-dicyclohexyl methane diisocyanate compound, be warming up to 65 DEG C, reaction 8h, obtain the base polyurethane prepolymer for use as of isocyanate group end-blocking, this performed polymer is cooled to 35 DEG C, add the butanone dilution of 60g, add 5.46g triethylamine again, during neutralization reaction 50min obtains and mixed solution, under high-speed stirring toward in and mixed solution in add 600g deionized water, emulsification 50min, add 1.5g quadrol again, continue high-speed stirring 50min, obtain aqueous polyurethane emulsion, by this aqueous polyurethane emulsion at 44 DEG C, underpressure distillation is except desolventizing, obtain the high moisture-inhibiting water-base polyurethane material that solid content is 25%, the vapor transfer rate recording fabric after this material is made textile coating agent is 5300g/m
2day, water pressure resistance are 64.7KPa.
Claims (6)
1. one kind high moisture-inhibiting water-base polyurethane material, it is characterized in that this material is made up of urethane resin and water, urethane resin is made up of each component of following weight percent: the long-chain polyols compound of 40wt% ~ 80wt%, 10wt% ~ 50wt% diisocyanate cpd, the anionic hydrophilic compounds of 1wt% ~ 10wt%, the low molecular compound of 0.05wt% ~ 5wt% hydroxyl, the quadrol of 1wt% ~ 5wt%; In the water-base polyurethane material be made up of urethane resin and water, the weight percent of water is 50wt% ~ 75wt%.
2. a preparation method for high moisture-inhibiting water-base polyurethane material, is characterized in that this preparation method is:
Long-chain polyols compound, anionic hydrophilic compounds and the low molecular compound containing hydroxyl are added in reactor simultaneously, at 70 ~ 90 DEG C, stir 0.5 ~ 1h mix to obtain glycol mixed solution, after this glycol mixed solution is cooled to 40 ~ 55 DEG C, add diisocyanate cpd, be warming up to 60 ~ 80 DEG C, reaction 6 ~ 8h, obtains the base polyurethane prepolymer for use as of isocyanate group end-blocking; This performed polymer is cooled to 15 ~ 40 DEG C, and to add with this performed polymer total mass ratio be that the butanone of 0.2:1 ~ 0.3:1 dilutes, the triethylamine that to add with anionic hydrophilic compounds mol ratio be again 0.9:1 ~ 1.1:1 carries out neutralization reaction 0.5 ~ 1h, in obtaining and mixed solution; Under high-speed stirring toward in and in mixed solution, to add with above-mentioned performed polymer total mass ratio be the deionized water of 1:1 ~ 3:1, emulsification 0.5 ~ 1h, then add quadrol and carry out chain extending reaction 0.5 ~ 1h, obtain aqueous polyurethane emulsion; By this aqueous polyurethane emulsion, at 40 ~ 50 DEG C, underpressure distillation is except desolventizing, and the weight percent keeping water in this water-base polyurethane material is 50wt% ~ 75wt%, obtains the high moisture-inhibiting water-base polyurethane material that solid content is 25wt% ~ 50wt%.
3. the high moisture-inhibiting water-base polyurethane material of one according to claim 1, is characterized in that molecular weight that described long-chain polyols compound is 40wt% ~ 80wt% by weight percent to be the polyoxyethylene glycol of 1000 ~ 3000 and the molecular weight of 20wt% ~ 60wt% is that the polytetrahydrofuran diol of 1000 ~ 3000 forms.
4. the high moisture-inhibiting water-base polyurethane material of one according to claim 1, is characterized in that described diisocyanate cpd is the one in hydrogenation of benzene dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
5. the high moisture-inhibiting water-base polyurethane material of one according to claim 1, is characterized in that described anionic hydrophilic compounds is the one in dimethylol propionic acid, dimethylolpropionic acid.
6. the high moisture-inhibiting water-base polyurethane material of one according to claim 1, it is characterized in that the low molecular compound of described hydroxyl is 1,4-butyleneglycol, TriMethylolPropane(TMP), 1,6-hexylene glycol, glycol ether, 3-methyl isophthalic acid, one or more the combination in 5-pentanediol.
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