CN118005884A - Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather - Google Patents
Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather Download PDFInfo
- Publication number
- CN118005884A CN118005884A CN202410411053.6A CN202410411053A CN118005884A CN 118005884 A CN118005884 A CN 118005884A CN 202410411053 A CN202410411053 A CN 202410411053A CN 118005884 A CN118005884 A CN 118005884A
- Authority
- CN
- China
- Prior art keywords
- water
- percent
- reduced
- polyurethane emulsion
- microfiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229920001410 Microfiber Polymers 0.000 title claims abstract description 82
- 239000003658 microfiber Substances 0.000 title claims abstract description 82
- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- 239000000839 emulsion Substances 0.000 title claims abstract description 65
- 239000010985 leather Substances 0.000 title claims abstract description 40
- 239000004970 Chain extender Substances 0.000 claims abstract description 43
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical group 0.000 claims abstract description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- -1 polyol compound Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DLVZBSZXZDGKQY-UHFFFAOYSA-N 2,2-dihydroxybutanoic acid Chemical compound CCC(O)(O)C(O)=O DLVZBSZXZDGKQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 63
- 238000002360 preparation method Methods 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 12
- 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 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920006264 polyurethane film Polymers 0.000 description 6
- 239000002649 leather substitute Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 101000974007 Homo sapiens Nucleosome assembly protein 1-like 3 Proteins 0.000 description 4
- 102100022398 Nucleosome assembly protein 1-like 3 Human genes 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 235000013372 meat Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a water-based polyurethane emulsion for water-reduced microfibers, which comprises the following raw materials in percentage by weight: 4.0 to 6.0 percent of diisocyanate, 16.0 to 20.0 percent of polyol compound, 0.4 to 1.0 percent of hydrophilic chain extender, 0.4 to 1.0 percent of reactive hydroxyl silicone oil, 0.1 to 0.4 percent of small molecular dihydric alcohol chain extender, 0.1 to 0.5 percent of amine chain extender, 0.002 to 0.004 percent of catalyst, 0.2 to 0.5 percent of neutralizer, 20 to 30 percent of organic solvent and 40 to 50 percent of water, wherein the total weight percent of the raw materials is 100 percent; the reactive hydroxyl silicone oil is one or two of single-end dihydroxy organic silicon and monohydroxy organic silicon with Y-shaped structures. The invention also discloses a preparation method of the water-based polyurethane emulsion for the water-reduced microfiber. The invention also discloses a water-reduced microfiber leather and a preparation method thereof. The polyurethane emulsion can lead the water-soluble sea-island fiber to be opened smoothly.
Description
Technical Field
The invention relates to the technical field of leather, in particular to water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather.
Background
The superfine fiber synthetic leather originally originates from Japan, is a polymer composite material of polyurethane resin and superfine fiber, structurally has a 'simulation' structure of leather, is used as a fourth-generation synthetic leather product, has high mechanical strength, soft and plump hand feeling and strong leather feel, and is an ideal substitute of natural leather.
The island microfiber synthetic leather is divided into a toluene drawn indefinite island microfiber and an alkali reduced definite island microfiber, wherein the toluene drawn indefinite island microfiber is mainly used in the market at present, solvent polyurethane resin is mainly adopted in the production and preparation process, and the island microfiber is split through a toluene solvent in the later stage to prepare the superfine fiber synthetic leather.
With the environmental protection requirement, the water-based polyurethane is adopted to impregnate the island fiber, and then toluene extraction or alkali liquor reduction is carried out on the fiber for fiber opening treatment, and the preparation process of the product does not use solvent polyurethane, but the toluene extraction uses an organic solvent, and a large amount of wastewater treatment is brought by alkali liquor reduction, so that the current product is difficult to be truly environment-friendly low-carbon microfiber leather.
With the progress of technology, water-soluble sea-island fibers taking polyvinyl alcohol as sea phase appear in the market at present, the water-soluble sea-island fibers are used as non-woven fabrics, and the fibers can be subjected to fiber opening treatment through hot water, but no proper aqueous PUD emulsion can be matched with the water-soluble sea-island fibers to prepare the microfiber synthetic leather in the market at present. After the traditional aqueous PUD emulsion contains water-soluble sea-island fibers and is dried, the fibers are not fully opened in later-stage high-temperature hot water, the fibers are thicker, the fiber opening efficiency is low, the hand feeling is poor, and the surface Mao Xiaocha cannot meet the requirements of products.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides aqueous polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather; according to the invention, single-end dihydroxy organic silicon or/and monohydroxy organic silicon with a Y-shaped structure is introduced into a polyurethane molecular chain, polyamine is used as a chain extender, and a post-chain extension method is adopted, so that the water repellent effect of the water-soluble sea-island fiber non-woven fabric impregnated with the water-soluble polyurethane emulsion after drying and forming can be effectively ensured, the compactness of the polyurethane molecular chain after film formation can be improved, the water resistance of a polyurethane film is improved, the water swelling property of the polyurethane film is reduced, and the problem that the water-soluble sea-island fiber is difficult to open due to hydrophilic swelling of polyurethane in the hot water fiber opening process is solved; the fiber opening efficiency of the water-soluble sea-island fiber can be greatly improved, the production and use requirements of the water-soluble sea-island fiber are met, and the prepared water-decrement microfiber leather has high mechanical property, good hand feeling and good rebound resilience.
The invention provides a water-based polyurethane emulsion for water-reduced microfibers, which comprises the following raw materials in percentage by weight: 4.0 to 6.0 percent of diisocyanate, 16.0 to 20.0 percent of polyol compound, 0.4 to 1.0 percent of hydrophilic chain extender, 0.4 to 1.0 percent of reactive hydroxyl silicone oil, 0.1 to 0.4 percent of small molecular dihydric alcohol chain extender, 0.1 to 0.5 percent of amine chain extender, 0.002 to 0.004 percent of catalyst, 0.2 to 0.5 percent of neutralizer, 20 to 30 percent of organic solvent and 40 to 50 percent of water, wherein the total weight percent of the raw materials is 100 percent;
the reactive hydroxyl silicone oil is one or two of single-end dihydroxy organic silicon and monohydroxy organic silicon with Y-shaped structures.
Preferably, the reactive hydroxy silicone oil has a number average molecular weight of 500-2000 g/mol.
Preferably, the polyol compound is one or two of polytetrahydrofuran diol and polycarbonate diol.
Preferably, the diisocyanate is an aliphatic diisocyanate.
Preferably, the aliphatic diisocyanate is one or two of isophorone diisocyanate and hexamethylene diisocyanate.
Preferably, the hydrophilic chain extender is one or two of dimethylolpropionic acid and dihydroxybutyric acid.
Preferably, the small molecular dihydric alcohol chain extender is one or more of ethylene glycol, 1, 4-butanediol and neopentyl glycol.
Preferably, the amine chain extender is a polyamine.
Preferably, the organic solvent is at least one of acetone and butanone.
The invention also provides a preparation method of the water-based polyurethane emulsion for the water-reduced microfiber, which comprises the following steps: and in an inert gas atmosphere, uniformly mixing a polyol compound, a micromolecular dihydric alcohol chain extender, a hydrophilic chain extender, diisocyanate and a catalyst, reacting, adding reactive hydroxyl silicone oil for continuous reaction, adding an organic solvent for viscosity reduction, adding a neutralizing agent for neutralization reaction, adding water for emulsification, adding an amine chain extender for continuous reaction, and removing the organic solvent to obtain the water-reduced microfiber aqueous polyurethane emulsion.
Preferably, the polyol compound, the micromolecular dihydric alcohol chain extender and the hydrophilic chain extender are uniformly mixed, dehydrated and cooled, and then uniformly mixed with the diisocyanate and the catalyst.
Preferably, the dehydration conditions are: vacuum dehydrating at 110-120deg.C for 1-2 hr.
Preferably, the temperature is reduced to 45-55 ℃.
Preferably, the reaction is carried out at 90-95℃for 1.5-2.5h.
Preferably, the reactive hydroxy silicone oil is added and the reaction is continued for 1.5-2.5h at 80-85 ℃.
Preferably, amine chain extenders are added and the reaction is continued for 0.5-1h at 20-25 ℃.
Preferably, the temperature is reduced to 30-40 ℃, and an organic solvent is added for viscosity reduction.
Preferably, the neutralization reaction is carried out at 30-40℃for 8-12min.
The invention also provides a water decrement microfiber leather, which comprises the following components: and the water-based polyurethane emulsion for the water-reduced microfiber.
Preferably, the temperature of the water is 80-100 ℃ when the water is reduced.
Preferably, the nonwoven fabric is a water-soluble sea-island fiber nonwoven fabric.
The invention also provides a preparation method of the water decrement microfiber leather, which comprises the following steps: and (3) taking the aqueous polyurethane emulsion for the water-reduced microfiber, regulating the viscosity, impregnating the non-woven fabric, drying, performing weight reduction treatment with water, washing with water, and drying to obtain the water-reduced microfiber leather.
Preferably, the viscosity is adjusted to 3000-5000 CPS.
Preferably, the decrement treatment is performed with water having a temperature of 80-100℃for 20-40min.
Advantageous effects
According to the invention, single-end dihydroxy organic silicon with a Y-shaped structure is introduced into a polyurethane molecular chain or single-end dihydroxy organic silicon and monohydroxy organic silicon with a Y-shaped structure are introduced, so that the side chain part and the end part in the polyurethane molecular chain contain water-repellent organic silicon chain segments, the water-repellent effect of the water-based polyurethane emulsion after the water-immersed island fiber non-woven fabric is dried and molded can be effectively ensured, and the problem of difficult fiber opening caused by hydrophilic swelling of polyurethane in the hot water fiber opening process of the water-soluble island fiber is avoided; the fiber opening efficiency of the water-soluble sea-island fiber can be greatly improved, the production and use requirements of the water-soluble sea-island fiber are met, and the prepared water-decrement microfiber leather has high mechanical property, good hand feeling and good rebound resilience.
The invention adopts polyamine as a chain extender and adopts a post-chain extension method to prepare the aqueous polyurethane emulsion, which can ensure the compactness of polyurethane molecular chains after film formation, reduce the water swelling property of polyurethane film, improve the water resistance of the polyurethane film and further promote the smooth opening of water-soluble sea-island fibers in hot water.
The aqueous polyurethane emulsion is prepared by adopting a stepwise prepolymerization process, and is used for preparing the water-reduced microfiber leather, so that the obtained microfiber leather not only has excellent mechanical properties and good hand feeling, but also realizes the environment-friendly preparation of the microfiber leather in a real sense.
Drawings
FIG. 1 is an electron microscopic image of water-reduced microfiber leather prepared using the emulsion of example 1.
FIG. 2 is an electron microscopic image of the water-reduced microfiber leather prepared using the emulsion of comparative example 1.
Detailed Description
The invention relates to a water-based polyurethane emulsion for water-reduced microfibers, which comprises the following raw materials in percentage by weight: 4.0 to 6.0 percent of diisocyanate, 16.0 to 20.0 percent of polyol compound, 0.4 to 1.0 percent of hydrophilic chain extender, 0.4 to 1.0 percent of reactive hydroxyl silicone oil, 0.1 to 0.4 percent of small molecular dihydric alcohol chain extender, 0.1 to 0.5 percent of amine chain extender, 0.002 to 0.004 percent of catalyst, 0.2 to 0.5 percent of neutralizer, 20 to 30 percent of organic solvent and 40 to 50 percent of water, wherein the total weight percent of the raw materials is 100 percent;
the reactive hydroxyl silicone oil is one or two of single-end dihydroxy organic silicon and monohydroxy organic silicon with Y-shaped structures.
When the reactive hydroxyl silicone oil is a mixture of single-end dihydroxy organic silicon and monohydroxy organic silicon with a Y-shaped structure, the weight ratio of the single-end dihydroxy organic silicon to the monohydroxy organic silicon with the Y-shaped structure is 1.5-2.5:1.
The single-end dihydroxy organosilicon with the Y-shaped structure can be: reactive hydroxy silicone oil 8866 (available from Japanese Kogyo) and the like.
The monohydroxy organosilicon may be: monohydroxy silicone oil 550 (available from enjing, su) and the like.
The raw materials of the aqueous polyurethane emulsion for water-reduced microfiber may further include: antioxidants, and the like.
The neutralizing agent can be one or two of triethylamine, triethanolamine and the like.
The antioxidant can be one or two of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -methylenebis (4-methyl-6-tert-butylphenol) and the like; the weight percentage of the antioxidant can be 0.016-0.03%.
The catalyst may be an organobismuth catalyst MB20 or the like.
Preferably, the reactive hydroxy silicone oil has a number average molecular weight of 500-2000 g/mol.
According to the invention, single-end dihydroxy organic silicon or/and monohydroxy organic silicon with a Y-shaped structure is introduced into a polyurethane molecular chain, so that a side chain part and a terminal part in the polyurethane molecular chain contain water-repellent organic silicon chain segments, the water-repellent effect of the water-based polyurethane emulsion after the water-soluble sea-island fiber non-woven fabric is soaked and dried and molded can be effectively ensured, and the problem of difficult fiber opening caused by hydrophilic swelling of polyurethane in the hot water fiber opening process of the water-soluble sea-island fiber is avoided; the fiber opening efficiency of the water-soluble sea-island fiber can be greatly improved, the production and use requirements of the water-soluble sea-island fiber are met, and the prepared water-decrement microfiber leather has high mechanical property, good hand feeling and good rebound resilience.
Preferably, the polyol compound is one or two of polytetrahydrofuran diol and polycarbonate diol.
When the polyol compound is a mixture of polytetrahydrofuran glycol and polycarbonate diol, the weight ratio of polytetrahydrofuran glycol to polycarbonate diol is 1.9-2.4:1.
Preferably, the diisocyanate is an aliphatic diisocyanate.
Preferably, the aliphatic diisocyanate is one or two of isophorone diisocyanate and hexamethylene diisocyanate.
When the diisocyanate is a mixture of isophorone diisocyanate and hexamethylene diisocyanate, the weight ratio of isophorone diisocyanate to hexamethylene diisocyanate is 7.5-11:1.
Preferably, the hydrophilic chain extender is one or two of dimethylolpropionic acid and dihydroxybutyric acid.
Preferably, the small molecular dihydric alcohol chain extender is one or more of ethylene glycol, 1, 4-butanediol and neopentyl glycol.
Preferably, the amine chain extender is a polyamine; more preferably, the amine chain extender is one or two of diethylenetriamine and triethylenetetramine.
The polyamine refers to an amine having three or more amino groups in the molecule.
Preferably, the organic solvent is at least one of acetone and butanone.
The invention also provides a preparation method of the water-based polyurethane emulsion for the water-reduced microfiber, which comprises the following steps: and in an inert gas atmosphere, uniformly mixing a polyol compound, a micromolecular dihydric alcohol chain extender, a hydrophilic chain extender, diisocyanate and a catalyst, reacting, adding reactive hydroxyl silicone oil for continuous reaction, adding an organic solvent for viscosity reduction, adding a neutralizing agent for neutralization reaction, adding water for emulsification, adding an amine chain extender for continuous reaction, and removing the organic solvent to obtain the water-reduced microfiber aqueous polyurethane emulsion.
The invention adopts polyamine as a chain extender and adopts a post-chain extension method to prepare the aqueous polyurethane emulsion, which can ensure the compactness of polyurethane molecular chains after film formation, reduce the water swelling property of polyurethane film, improve the water resistance of the polyurethane film and further promote the smooth opening of water-soluble sea-island fibers in hot water.
The aqueous polyurethane emulsion is prepared by adopting a stepwise prepolymerization process, and is used for preparing the water-reduced microfiber leather, so that the obtained microfiber leather not only has excellent mechanical properties and good hand feeling, but also realizes the environment-friendly preparation of the microfiber leather in a real sense.
Preferably, the polyol compound, the micromolecular dihydric alcohol chain extender and the hydrophilic chain extender are uniformly mixed, dehydrated and cooled, and then uniformly mixed with the diisocyanate and the catalyst.
Preferably, the dehydration conditions are: vacuum dehydrating at 110-120deg.C for 1-2 hr.
Preferably, the temperature is reduced to 45-55 ℃.
Preferably, the reaction is carried out at 90-95℃for 1.5-2.5h.
Preferably, the reactive hydroxy silicone oil is added and the reaction is continued for 1.5-2.5h at 80-85 ℃.
Preferably, amine chain extenders are added and the reaction is continued for 0.5-1h at 20-25 ℃.
Preferably, the temperature is reduced to 30-40 ℃, and an organic solvent is added for viscosity reduction.
Preferably, the neutralization reaction is carried out at 30-40℃for 8-12min.
The invention also provides a water decrement microfiber leather, which comprises the following components: and the water-based polyurethane emulsion for the water-reduced microfiber.
Preferably, the temperature of the water is 80-100 ℃ when the water is reduced.
Preferably, the nonwoven fabric is a water-soluble sea-island fiber nonwoven fabric.
The water-soluble sea-island fiber can be sea-island fiber with water-soluble polyvinyl alcohol as sea phase, and the island phase can be nylon or terylene.
The invention also provides a preparation method of the water decrement microfiber leather, which comprises the following steps: and (3) taking the aqueous polyurethane emulsion for the water-reduced microfiber, regulating the viscosity, impregnating the non-woven fabric, drying, performing weight reduction treatment with water, washing with water, and drying to obtain the water-reduced microfiber leather.
Preferably, the viscosity is adjusted to 3000-5000 CPS.
The viscosity is a viscosity at 25 ℃.
The viscosity is adjusted by adding a thickener to the aqueous polyurethane emulsion.
Preferably, the decrement treatment is performed with water having a temperature of 80-100℃for 20-40min.
The water may be deionized water, purified water, or the like.
The technical scheme of the invention is described in detail through specific embodiments.
The raw material information used in the following examples and comparative examples is shown in table 1.
TABLE 1 raw material information
| Name of the name | Manufacturer' s |
| Polytetrahydrofuran diol with molecular weight of 2000 (PTMG-2000) | Taiwan Dalian chemical industry Co., ltd |
| Polycarbonate diol with molecular weight of 2000 (PCD-5652) | Xuehua chemical prescription |
| Hexamethylene Diisocyanate (HDI) | Wanhua chemistry |
| Isophorone diisocyanate (IPDI) | Wanhua chemistry |
| Single-end double-hydroxyl organic silicon with Y-shaped structure (reactive hydroxyl silicone oil 8866) | Japanese Xinyue (Chinese character) |
| Monohydroxy silicone oil 550 | Suzhou Enjing |
| Dimethylolpropionic acid (DMPA) | Swedish Pasteur |
Example 1
An aqueous polyurethane emulsion for water-reducing microfibers, which comprises the following raw materials: 7g of hexamethylene diisocyanate, 77g of isophorone diisocyanate, 190g of PTMG-2000, 100g of PCD-5652, 8866 g of reactive hydroxy silicone oil, 7g of dimethylolpropionic acid, 2g of 1, 4-butanediol, 4g of diethylenetriamine, 20.05 g of organobismuth catalyst MB, 5.2g of neutralizer triethylamine, 0.3g of antioxidant I-1010, 380g of acetone and 750g of deionized water.
The preparation method of the water-based polyurethane emulsion for the water-reduced microfiber comprises the following steps:
Adding PTMG-2000, PCD-5652, 1, 4-butanediol, DMPA and antioxidant I-1010 into a reaction bottle, decompressing and dehydrating for 2 hours at 110 ℃, cooling to 50 ℃, then adding HDI and IPDI under the protection of nitrogen, reacting for 2 hours at the constant temperature of 90 ℃, and adding an organic bismuth catalyst MB20 in the reaction process;
then adding reactive hydroxyl silicone oil 8866, regulating the temperature to 80 ℃ for continuous reaction for 2 hours, sampling after the reaction time is up, measuring NCO% by adopting a di-n-butylamine titration method, stopping the reaction when the detection value of NCO% is lower than a theoretical value, cooling to 30 ℃, adding acetone for reducing the viscosity, adding a neutralizing agent triethylamine, and stirring at 30 ℃ for neutralization reaction for 10 minutes;
Adding deionized water under high-speed stirring at 1500rpm, and emulsifying and dispersing; then diethylenetriamine is added, and the mixture is continuously stirred at 20 ℃ for chain extension reaction for 0.5h; finally, acetone is removed by reduced pressure distillation at 40 ℃ to obtain the water-based polyurethane emulsion for the water-reduced microfiber.
Example 2
An aqueous polyurethane emulsion for water-reducing microfibers, which comprises the following raw materials: 10g of hexamethylene diisocyanate, 75g of isophorone diisocyanate, 2000 g of PTMG-2000 g, 85g of PCD-5652, 8866 g of reactive hydroxyl silicone oil, 550 g of monohydroxy silicone oil, 7g of dimethylolpropionic acid, 2g of 1, 4-butanediol, 4.5g of diethylenetriamine, 20.05 g of organobismuth catalyst MB, 5.2g of neutralizer triethylamine, 0.3g of antioxidant I-1010, 380g of acetone and 750g of deionized water.
The preparation method of the water-based polyurethane emulsion for the water-reduced microfiber comprises the following steps:
Adding PTMG-2000, PCD-5652, 1, 4-butanediol, DMPA and antioxidant I-1010 into a reaction bottle, decompressing and dehydrating for 1h at 120 ℃, cooling to 50 ℃, then adding HDI and IPDI under the protection of nitrogen, reacting for 2h at the constant temperature of 95 ℃, and adding an organic bismuth catalyst MB20 in the reaction process;
Then adding reactive hydroxyl silicone oil 8866 and monohydroxy silicone oil 550, regulating the temperature to 85 ℃ for continuous reaction for 2 hours, sampling after the reaction time is up, adopting a di-n-butylamine titration method to measure NCO%, stopping the reaction when the detection value of NCO% is lower than the theoretical value, cooling to 40 ℃, adding acetone for reducing the viscosity, adding a neutralizing agent triethylamine, and stirring at 40 ℃ for neutralization reaction for 10 minutes;
then adding deionized water under high-speed stirring at 1000rpm, and performing emulsification and dispersion; then diethylenetriamine is added, and the mixture is continuously stirred at 25 ℃ for chain extension reaction for 0.5h; finally, acetone is removed by reduced pressure distillation at 55 ℃ to obtain the water-based polyurethane emulsion for the water-reduced microfiber.
Example 3
An aqueous polyurethane emulsion for water-reducing microfibers, which comprises the following raw materials: 10g of hexamethylene diisocyanate, 75g of isophorone diisocyanate, 2000 g of PTMG-2000 g, 85g of PCD-5652, 8866 g of reactive hydroxyl silicone oil, 550 g of monohydroxy silicone oil, 7g of dimethylolpropionic acid, 2g of 1, 4-butanediol, 3.8g of triethylene tetramine, 20.05 g of organobismuth catalyst MB, 5.2g of neutralizing agent triethylamine, 0.3g of antioxidant I-1010, 380g of acetone and 750g of deionized water.
The preparation method of the water-based polyurethane emulsion for the water-reduced microfiber comprises the following steps:
Adding PTMG-2000, PCD-5652, 1, 4-butanediol, DMPA and antioxidant I-1010 into a reaction bottle, decompressing and dehydrating for 1.5h at 115 ℃, cooling to 50 ℃, then adding HDI and IPDI under the protection of nitrogen, reacting for 2h at 92 ℃ at constant temperature, and adding an organobismuth catalyst MB20 in the reaction process;
Then adding reactive hydroxyl silicone oil 8866 and monohydroxy silicone oil 550, regulating the temperature to 82 ℃ for continuous reaction for 2 hours, sampling after the reaction time is up, adopting a di-n-butylamine titration method to measure NCO%, stopping the reaction when the detection value of NCO% is lower than the theoretical value, cooling to 35 ℃, adding acetone for reducing the viscosity, adding a neutralizing agent triethylamine, and stirring at 35 ℃ for neutralization reaction for 10 minutes;
Adding deionized water under high-speed stirring at 1200rpm, and emulsifying and dispersing; then triethylene tetramine is added, and the mixture is continuously stirred at 22 ℃ for chain extension reaction for 0.5h; finally, the acetone is removed by reduced pressure distillation at 50 ℃ to obtain the water-based polyurethane emulsion for the water-reduced microfiber.
Comparative example 1
An aqueous polyurethane emulsion which did not contain reactive hydroxy silicone oil 8866 and which had a PTMG-2000 of 200g was prepared in the same manner as in example 1.
Comparative example 2
An aqueous polyurethane emulsion was prepared by replacing 4.5g of diethylenetriamine with 3.5g of ethylenediamine, and the procedure of example 2 was followed.
Comparative example 3
An aqueous polyurethane emulsion which does not contain reactive hydroxyl silicone oil 8866 and monohydroxy silicone oil 550, and which is prepared by replacing "3.8 g of triethylene tetramine" with "3.5 g of ethylenediamine" in the same manner as in example 2.
The polyurethane emulsions of examples 1 to 3 and comparative examples 1 to 3 were taken and conventional aqueous polyurethane emulsions for microfiber were purchased from the market as Hongdeli 203, bosida 305 (sequentially recorded as comparative example 4, comparative example 5), and a thickener was added to each emulsion (0.3 to 0.5 parts of thickener was added per 100 parts of emulsion by weight) so that the viscosity of the solution was 4000 CPS/25 ℃ to obtain each working slurry; then respectively soaking the water-soluble sea-island fiber non-woven fabrics with each group of working pulp, drying for 30min in a baking oven at 120-130 ℃, taking out, putting into hot water at 90 ℃ for carrying out reduction treatment for 30min to obtain leather samples, taking out the leather samples, washing with water, and drying to obtain the water reduction microfiber leather.
The performance of each group of the water-reduced microfiber leather was measured, and the results are shown in Table 2 and FIGS. 1-2.
FIG. 1 is an electron microscopic image of a water-reduced microfiber leather prepared using the emulsion of example 1; FIG. 2 is an electron microscopic image of the water-reduced microfiber leather prepared using the emulsion of comparative example 1.
As can be seen from fig. 1-2: the microfiber leather prepared in example 1 had significantly finer fibers, while the microfiber leather prepared in comparative example 1 had more unopened fibers, most of which were unopened.
TABLE 2 detection results
| Grouping | Hand feel | Whether or not the surface fiber is completely opened |
| Example 1 | Good meat feel and good rebound | The bundle-shaped fibers are obvious, and the fibers are completely opened |
| Comparative example 1 | General feeling of stiffness | The fiber is more than that of the fiber |
| Example 2 | Good meat feel and good rebound | The bundle-shaped fibers are obvious, and the fibers are completely opened |
| Comparative example 2 | The hand feeling is general | The fiber is more than that of the fiber |
| Example 3 | Good meat feel and good rebound | The bundle-shaped fibers are obvious, and the fibers are completely opened |
| Comparative example 3 | Stiff hand feel | Most of the fibers are not opened |
| Comparative example 4 | Stiff hand feel | Most of the fibers are not opened |
| Comparative example 5 | Stiff hand feel | Most of the fibers are not opened |
As can be seen from table 2: single-end dihydroxy organic silicon with a Y-shaped structure or single-end dihydroxy organic silicon and monohydroxy organic silicon with a Y-shaped structure are added independently, the fiber opening effect after the obtained aqueous polyurethane solution is impregnated with the microfiber is general, the hand feeling of the obtained water-reduced microfiber leather is general, and the surface hairiness is general; the aqueous polyurethane solution can promote the fiber opening of the water-soluble sea-island fiber by adding the polyamine as the chain extender, and the obtained water-decrement microfiber leather has good hand feeling, good rebound and good surface hair effect.
The polyurethane emulsions of examples 1-3 and comparative examples 1-3 were taken and conventional aqueous polyurethane emulsions for microfiber were purchased from the market as Hongdeli 203, bosida 305 (sequentially recorded as comparative example 4, comparative example 5), and a thickener was added to each emulsion so that the viscosity of the solution was 2500 CPS/25 ℃, to obtain each working slurry; each group of working slurries was coated on a glass plate, dried films were cut to 30mm by 30mm, the initial weight M1 was weighed, then placed in hot water at 90 ℃ for 30min, the surface water was wiped off, the weight M2 was weighed, and the water absorption= (M2-M1)/M1 by 100% was calculated, and the detection results were shown in table 3.
TABLE 3 Water absorption detection results
| Grouping | Water absorption percentage% |
| Example 1 | 1.2 |
| Comparative example 1 | 4.8 |
| Example 2 | 1.0 |
| Comparative example 2 | 5.2 |
| Example 3 | 0.9 |
| Comparative example 3 | 8.5 |
| Comparative example 4 | 7.8 |
| Comparative example 5 | 8.4 |
As can be seen from table 3: single-end dihydroxy organic silicon with a Y-shaped structure or single-end dihydroxy organic silicon and monohydroxy organic silicon with a Y-shaped structure are added independently, so that the water resistance of the waterborne polyurethane can be improved, and the water swelling performance of the waterborne polyurethane can be reduced; by adding polyamine as a chain extender, the water resistance of the waterborne polyurethane can be further improved, and the water swelling performance of the waterborne polyurethane can be reduced.
From the results of FIGS. 1-2 and tables 2-3, it can be seen that: the aqueous polyurethane emulsion is applied to the field of water decrement microfibers, so that the water-soluble sea-island fiber can be smoothly opened in hot water, and the prepared microfibers have good hand feeling and good rebound.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The aqueous polyurethane emulsion for the water-reduced microfiber is characterized by comprising the following raw materials in percentage by weight: 4.0 to 6.0 percent of diisocyanate, 16.0 to 20.0 percent of polyol compound, 0.4 to 1.0 percent of hydrophilic chain extender, 0.4 to 1.0 percent of reactive hydroxyl silicone oil, 0.1 to 0.4 percent of small molecular dihydric alcohol chain extender, 0.1 to 0.5 percent of amine chain extender, 0.002 to 0.004 percent of catalyst, 0.2 to 0.5 percent of neutralizer, 20 to 30 percent of organic solvent and 40 to 50 percent of water, wherein the total weight percent of the raw materials is 100 percent;
the reactive hydroxyl silicone oil is one or two of single-end dihydroxy organic silicon and monohydroxy organic silicon with Y-shaped structures.
2. The aqueous polyurethane emulsion for water-reduced microfibers of claim 1 wherein the reactive hydroxyl silicone oil has a number average molecular weight of 500 to 2000 g/mol.
3. The aqueous polyurethane emulsion for reduced water microfiber of claim 1 wherein the polyol compound is one or both of polytetrahydrofuran diol and polycarbonate diol.
4. The aqueous polyurethane emulsion for water-reduced microfibers of claim 1 wherein the diisocyanate is an aliphatic diisocyanate.
5. The aqueous polyurethane emulsion for reduced water microfibers of claim 1, wherein the hydrophilic chain extender is one or both of dimethylolpropionic acid and dihydroxybutyric acid; the amine chain extender is polyamine.
6. A method for preparing the aqueous polyurethane emulsion for water-reduced microfibers according to any one of claims 1 to 5, comprising the steps of: and in an inert gas atmosphere, uniformly mixing a polyol compound, a micromolecular dihydric alcohol chain extender, a hydrophilic chain extender, diisocyanate and a catalyst, reacting, adding reactive hydroxyl silicone oil for continuous reaction, adding an organic solvent for viscosity reduction, adding a neutralizing agent for neutralization reaction, adding water for emulsification, adding an amine chain extender for continuous reaction, and removing the organic solvent to obtain the water-reduced microfiber aqueous polyurethane emulsion.
7. The method for preparing the aqueous polyurethane emulsion for the water-reduced microfiber, according to claim 6, wherein the polyol compound, the small-molecule dihydric alcohol chain extender and the hydrophilic chain extender are uniformly mixed, dehydrated and cooled, and then uniformly mixed with the diisocyanate and the catalyst.
8. The method for preparing an aqueous polyurethane emulsion for water-reduced microfibers according to claim 6, wherein the reaction is carried out at 90 to 95 ℃ for 1.5 to 2.5 hours; adding reactive hydroxyl silicone oil, and continuing to react for 1.5-2.5h at 80-85 ℃.
9. A water-reduced microfiber leather, comprising: a nonwoven fabric and the aqueous polyurethane emulsion for water-reduced microfibers according to any one of claims 1 to 5.
10. A method for preparing the water-reduced microfiber leather according to claim 9, comprising the steps of: the aqueous polyurethane emulsion for water-reduced microfiber according to any one of claims 1 to 5, wherein the aqueous polyurethane emulsion is used for adjusting the viscosity, and then the aqueous polyurethane emulsion is used for impregnating a nonwoven fabric, drying, and then the water-reduced microfiber leather is obtained by subjecting the nonwoven fabric to a reduction treatment with water, washing with water and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410411053.6A CN118005884B (en) | 2024-04-08 | 2024-04-08 | Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410411053.6A CN118005884B (en) | 2024-04-08 | 2024-04-08 | Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118005884A true CN118005884A (en) | 2024-05-10 |
| CN118005884B CN118005884B (en) | 2024-07-02 |
Family
ID=90954300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410411053.6A Active CN118005884B (en) | 2024-04-08 | 2024-04-08 | Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118005884B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| CN108129633A (en) * | 2017-12-14 | 2018-06-08 | 上海华峰新材料研发科技有限公司 | High bright minute surface polyurethane resin of folding and its preparation method and application |
| CN109134819A (en) * | 2018-03-15 | 2019-01-04 | 浙江德美博士达高分子材料有限公司 | Determine the preparation method of the water-base resin of island microfiber synthetic leather impregnation |
| CN110951030A (en) * | 2019-12-11 | 2020-04-03 | 上海华峰超纤科技股份有限公司 | Low-temperature-resistant and wear-resistant non-yellowing polyurethane resin and superfine fiber synthetic leather prepared from same |
| CN111909351A (en) * | 2020-06-23 | 2020-11-10 | 明新孟诺卡(浙江)新材料有限公司 | Synthetic method and application of waterborne polyurethane for microfiber impregnation |
| CN112724347A (en) * | 2020-12-28 | 2021-04-30 | 上海汇得科技股份有限公司 | Bio-based waterborne polyurethane resin and preparation method and application thereof |
| CN113929860A (en) * | 2021-10-22 | 2022-01-14 | 旭川化学（苏州）有限公司 | Water-based polyurethane resin emulsion for microfiber impregnation and preparation method and application thereof |
| CN114292383A (en) * | 2022-02-14 | 2022-04-08 | 山东天庆科技发展有限公司 | Alkali deweighting resin for water-based microfiber synthetic leather and preparation method and application thereof |
| CN115197395A (en) * | 2022-08-31 | 2022-10-18 | 嘉兴学院 | Aqueous polyurethane for impregnation of microfiber leather and preparation method and application thereof |
| CN116143994A (en) * | 2022-12-29 | 2023-05-23 | 广州海豚新材料有限公司 | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather |
| CN117362573A (en) * | 2023-09-26 | 2024-01-09 | 齐鲁工业大学(山东省科学院) | Preparation method and application of aqueous resin for microfiber impregnation |
-
2024
- 2024-04-08 CN CN202410411053.6A patent/CN118005884B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086740A (en) * | 2014-07-09 | 2014-10-08 | 温州柯莱恩科技有限公司 | Method for preparing organic silicon graft modified polyurethane resin for synthetic leather |
| CN108129633A (en) * | 2017-12-14 | 2018-06-08 | 上海华峰新材料研发科技有限公司 | High bright minute surface polyurethane resin of folding and its preparation method and application |
| CN109134819A (en) * | 2018-03-15 | 2019-01-04 | 浙江德美博士达高分子材料有限公司 | Determine the preparation method of the water-base resin of island microfiber synthetic leather impregnation |
| CN110951030A (en) * | 2019-12-11 | 2020-04-03 | 上海华峰超纤科技股份有限公司 | Low-temperature-resistant and wear-resistant non-yellowing polyurethane resin and superfine fiber synthetic leather prepared from same |
| CN111909351A (en) * | 2020-06-23 | 2020-11-10 | 明新孟诺卡(浙江)新材料有限公司 | Synthetic method and application of waterborne polyurethane for microfiber impregnation |
| CN112724347A (en) * | 2020-12-28 | 2021-04-30 | 上海汇得科技股份有限公司 | Bio-based waterborne polyurethane resin and preparation method and application thereof |
| CN113929860A (en) * | 2021-10-22 | 2022-01-14 | 旭川化学（苏州）有限公司 | Water-based polyurethane resin emulsion for microfiber impregnation and preparation method and application thereof |
| CN114292383A (en) * | 2022-02-14 | 2022-04-08 | 山东天庆科技发展有限公司 | Alkali deweighting resin for water-based microfiber synthetic leather and preparation method and application thereof |
| CN115197395A (en) * | 2022-08-31 | 2022-10-18 | 嘉兴学院 | Aqueous polyurethane for impregnation of microfiber leather and preparation method and application thereof |
| CN116143994A (en) * | 2022-12-29 | 2023-05-23 | 广州海豚新材料有限公司 | Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather |
| CN117362573A (en) * | 2023-09-26 | 2024-01-09 | 齐鲁工业大学(山东省科学院) | Preparation method and application of aqueous resin for microfiber impregnation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118005884B (en) | 2024-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087286B (en) | Waterborne polyurethane elastic dispersion and preparation method thereof | |
| CN105732938B (en) | A kind of preparation method of polyester polyether type aqueous polyurethane leather finishing agent | |
| CN110835401B (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN111909351A (en) | Synthetic method and application of waterborne polyurethane for microfiber impregnation | |
| CN112724347B (en) | Bio-based waterborne polyurethane resin and preparation method and application thereof | |
| CN111733616B (en) | Polyurethane resin for polyester fixed island microfiber and preparation method thereof | |
| CN113338051A (en) | Preparation method of solvent-free waterborne polyurethane microfiber synthetic leather with high R value | |
| CN112409564A (en) | Non-desolventizing water-based nonionic polyurethane and preparation method thereof | |
| KR101860708B1 (en) | Water-dispersive polyurethane resin composition for dip coating of suede and its manufacturing process | |
| CN112391841A (en) | Method for manufacturing anti-wrinkle fabric | |
| CN110669197A (en) | Low-gloss body extinction type waterborne polyurethane resin and preparation method thereof | |
| CN114456348A (en) | Preparation method of waterborne polyurethane for organic silicon modified polyester polyether type leather finishing | |
| CN112321794A (en) | Self-extinction water-based polyurethane resin for PVC gloves, coating agent and preparation method | |
| CN113881008A (en) | Solvent type polyurethane resin for suede microfiber dyeing and preparation method thereof | |
| CN105019248B (en) | The preparation method of cationoid reaction type environment-friendlyfabric fabric stiffening agent | |
| CN118005884B (en) | Water-based polyurethane emulsion for water-reduced microfiber and water-reduced microfiber leather | |
| CN111533875B (en) | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating | |
| CN111732708A (en) | Soft high-resilience aqueous polyurethane resin and preparation method and application thereof | |
| CN113152110A (en) | Environment-friendly polyurethane synthetic leather for sofa furniture and preparation method thereof | |
| CN112521581B (en) | Waterborne polyurethane surface layer resin for synthetic leather and preparation method and application thereof | |
| CN113402691B (en) | Modified waterborne polyurethane and preparation method and application thereof | |
| CN107857869B (en) | Aqueous polyurethane and its preparation method and application | |
| CN113372530B (en) | Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base | |
| CN113929860B (en) | Aqueous polyurethane resin emulsion for microfiber impregnation and preparation method and application thereof | |
| CN112900107B (en) | Waterborne polyurethane/organic silicon composite mirror leather and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |