CN106947048A - It is a kind of for waterborne polyurethane resin of aqueous clothing leather bass and preparation method thereof - Google Patents
It is a kind of for waterborne polyurethane resin of aqueous clothing leather bass and preparation method thereof Download PDFInfo
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- CN106947048A CN106947048A CN201710240277.5A CN201710240277A CN106947048A CN 106947048 A CN106947048 A CN 106947048A CN 201710240277 A CN201710240277 A CN 201710240277A CN 106947048 A CN106947048 A CN 106947048A
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- polyurethane resin
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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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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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
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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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
- C08G18/61—Polysiloxanes
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of for waterborne polyurethane resin of aqueous clothing leather bass and preparation method thereof, and the waterborne polyurethane resin includes following raw material components and parts by weight：70~85 parts of macromolecular polyol；10~20 parts of polyisocyanates；1.5~3.5 parts of hydrophilic chain extender；0.5~2 part of small molecule alcohol chain extender；6~25 parts of amine chain extender；0.01~0.5 part of catalyst；2~5 parts of salt forming agent.The present invention is using the larger ehter bond macromolecular polyol of molecular weight so that waterborne polyurethane resin possesses relatively low modulus and soft feel；The amine chain extender that the present invention is used is polyetheramine, compared with other amine chain extenders, the main chain of polyetheramine is polyether structure, so that the feel of aqueous polyurethane is more soft, and polyetheramine molecular weight is larger, the solid content of waterborne polyurethane resin is substantially increased, and then improves the richness of waterborne polyurethane resin.
Description
Technical field
The present invention relates to high molecular polymer field, a kind of aqueous poly- ammonia for aqueous clothing leather bass is specifically disclosed
Ester resin and preparation method thereof.
Background technology
Current solvent-borne type clothing leather bass has used substantial amounts of organic solvent DMF in the fabrication process, not only to environment
Pollution is caused, and the solvent remained in product also endangers the health of consumer.Waterborne polyurethane resin be using water as point
Dispersion media, in process without toxic organic solvents, it is to avoid the pollution to environment and the health hazard to operating personnel.
Waterborne polyurethane resin is widely applied to clothing leather bass field, and Waterborne synthetic leather bass is organic molten without benzene homologues, DMF etc.
Agent, has the advantages that asepsis environment-protecting, is liked by more and more consumers.But due to being used aqueous poly- ammonia by clothing leather bass
Limited in ester resin technology, cause aqueous clothing leather bass development to be restricted, especially in Boardy Feeling, clothing leather close structure
The problems such as degree difference and poor air permeability.Therefore, need badly and work out what a kind of waterborne polyurethane resin solution clothing leather bass was present
Above mentioned problem.
The content of the invention
Gather it is an object of the invention to the defect for overcoming prior art there is provided a kind of for the aqueous of aqueous clothing leather bass
Urethane resin and preparation method thereof, the coating bubble of the clothing leather bass prepared by the waterborne polyurethane resin is empty uniform and stable, clothes
Dress leather close structure is careful, soft, with excellent richness, gas permeability, higher peel strength and excellent resistance to song
Folding endurance energy.
In order to realize object above and other purposes, the present invention including following technical scheme by realizing：A kind of water
Property polyurethane resin, including following raw material components and parts by weight：
Preferably, the macromolecular polyol is 75~80 parts.
Preferably, the polyisocyanates is 13~17 parts.
Preferably, the hydrophilic chain extender is 2~3 parts.
Preferably, the small molecule alcohol chain extender is 1~1.5 part.
Preferably, the amine chain extender is 8~25 parts.
Preferably, the catalyst is 0.1~0.3 part.
Preferably, the salt forming agent is 3~4 parts.
Preferably, the macromolecular polyol includes PolyTHF ethoxylated polyhydric alcohol, polyethylene oxide polyol, polycyclic oxygen
Any one or more in oxide polyol, polyesterether polyols and polysiloxane polyhydric alcohol.
Preferably, the molecular weight of the macromolecular polyol is 2500-4500.
Preferably, the isocyanates includes toluene di-isocyanate(TDI), IPDI, diphenyl methane two
Isocyanates, hexamethylene diisocyanate, XDI, many benzene of naphthalene -1,5- diisocyanate polymethylenes
Based isocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate, the isocyanide of dicyclohexyl methyl hydride two
Any one or more in acid esters.
Preferably, the hydrophilic chain extender includes dihydromethyl propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxy
Any one or more in methyloctanoic acid.
Preferably, the small molecule alcohol chain extender include ethylene glycol, 2- methyl isophthalic acids, ammediol, diglycol,
1,4- butanediols, 2,3- butanediols, 1,6-HD, neopentyl glycol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane, two
Any one or more in methylol hexamethylene.
Preferably, the amine chain extender is polyetheramine.
Preferably, the molecular weight of the polyetheramine is 230~5000.
It is highly preferred that the molecular weight of the polyetheramine is 1800~2300.
Preferably, the catalyst elects organic bismuth catalyst as.
The catalyst is selected from organo-bismuth Coscat83, organo-bismuth 1610, organo-bismuth 2010, organo-bismuth 2810, organo-bismuth
Any one or more in 2808.
Preferably, the salt forming agent includes any one in triethylamine, ammoniacal liquor and NaOH or a variety of.
The present invention discloses a kind of side for preparing the waterborne polyurethane resin for aqueous clothing leather bass as described above
Method, comprises the following steps：The polyalcohol and the polyisocyanates react 2~3h at 85~95 DEG C；Add the parent
Water chain extender and the small molecule alcohol chain extender react 1.5~2.5h at 75~85 DEG C；Then the catalyst is added,
2~3h is reacted at 65~75 DEG C, -5~5 DEG C is cooled to and adds the salt forming agent neutralization；The amine chain extension is added after adding water
Agent, vacuum distillation obtains waterborne polyurethane resin.
Preferably, acetone is added while adding the catalyst.
The viscosity for acting as adjusting reaction solution of acetone.The addition of acetone can need to take the circumstances into consideration to add according to reaction.Institute
State acetone and be distilled removing in the vacuum distillation stage.
Preferably, the solid content of the aqueous polyurethane is 50-55%.
The invention also discloses it is a kind of as above-mentioned waterborne polyurethane resin aqueous clothing leather bass wet processing should
With.
Preferably, the wet processing of the aqueous clothing leather bass comprises the following steps：By 100 parts of above-mentioned aqueous polyurethanes
0.1-2 parts of wetting agents, 0.2-2.0 parts of filling powders, 0.2-2.5 parts of foaming are added under 500-800 revs/min of high speed shear
Agent, 0.1-0.5 portions of foam stabilizers, foam to 1.5-2.0 times of original volume, and the hair that viscosity is 15000mpas-18000mpas is made
Steep slurry；Base fabric is plated, is then applied in base fabric and is covered with foamed slurry, the base fabric for coating foamed slurry is then passed through into solidification
Solidification liquid in groove is condensed, and aqueous polyurethane is demulsified and is formed porous packing with filling powder, then passes through washing
Groove is cleaned, and 1.5-3h is dried in the baking oven for being subsequently placed in 100-120 DEG C, obtains aqueous clothing leather bass.
Preferably, the solidification liquid is the one or more in formic acid, acetic acid, aqueous hydrochloric acid solution, the matter of the solidification liquid
Amount concentration is 2%-5%.
In summary, the present invention provides a kind of waterborne polyurethane resin and its preparation side for aqueous clothing leather bass
Method, its advantage is：
The present invention is using the larger ehter bond macromolecular polyol of molecular weight so that waterborne polyurethane resin possesses relatively low mould
Amount and soft feel；The amine chain extender that the present invention is used is polyetheramine, compared with other amine chain extenders, the master of polyetheramine
Chain is polyether structure so that the feel of aqueous polyurethane is more soft, and polyetheramine molecular weight is larger, in demand same substance
In the case of the amino of amount, its quality is 5-80 times of other amines, substantially increases the solid content of waterborne polyurethane resin, and then
Improve the richness of waterborne polyurethane resin.The clothing leather bass prepared by waterborne polyurethane resin has feel hand
Without organic solvents such as benzene homologues, DMF in the high advantage of soft, richness, also, clothing leather bass, it is to avoid the pollution to environment
With the harm of health.
Embodiment
The present invention is expanded on further with reference to embodiment.It should be understood that embodiment is merely to illustrate the present invention, and it is unrestricted
The scope of the present invention.
Embodiment 1
80g PolyTHF ethoxylated polyhydric alcohol (molecular weight is 3000) is dehydrated 1h at 105 DEG C, 50 DEG C are then cooled to,
15g toluene di-isocyanate(TDI) is added, 90 DEG C of insulation reactions are warming up to 3 hours, NCO content is determined within two hours, reaches theoretical value
After be cooled to 50 DEG C, then add 2g dimethylolpropionic acids, 1.5g ethylene glycol and react 2h at 80 DEG C, be cooled to 50 DEG C, then
0.2g organo-bismuth Coscat83 and 2ml acetone adjustment viscosity are added, 2.5h is reacted at 70 DEG C, reaction terminates to determine NCO content,
Then 0 DEG C is cooled to, the triethylamine for adding 2.32g is neutralized, neutralizes after 30min, deionized water is added under high speed shear, point
2min is dissipated, the acetone in 10g polyetheramine (molecular weight is 2000), vacuum distillation removing system is then slowly added into, that is, obtains
Waterborne polyurethane resin sample 1.
Embodiment 2
78g polyethylene oxide polyol (molecular weight is 3000) is dehydrated 1h at 105 DEG C, 50 DEG C are then cooled to, plus
Enter 15g IPDI, be warming up to 90 DEG C of insulation reactions 3 hours, determine NCO content within two hours, reach theory
50 DEG C are cooled to after value, 2g dimethylolpropionic acids, 1.5g glycerine is then added and reacts 2h at 80 DEG C, be cooled to 50 DEG C, then
0.15g organo-bismuths 1610 and 2ml acetone adjustment viscosity are added, 2.5h is reacted at 70 DEG C, reaction terminates to determine NCO content, so
After be cooled to 0 DEG C, the triethylamine for adding 2.12g is neutralized, and neutralizes after 30min, deionized water is added under high speed shear, scattered
2min, is then slowly added into the acetone in 20g polyetheramine (molecular weight is 2000), vacuum distillation removing system, that is, obtains water
Property polyurethane resin sample 2.
Embodiment 3
75g polyesterether polyols (molecular weight is 3000) are dehydrated 1h at 105 DEG C, 50 DEG C are then cooled to, 15g is added
1, hexamethylene-diisocyanate is warming up to 90 DEG C of insulation reactions 3 hours, determines NCO content within two hours, reaches and cool after theoretical value
To 50 DEG C, then add 2g dihydroxymethyls octanoic acid, 1.5g ethylene glycol and react 2h at 80 DEG C, be cooled to 50 DEG C, then add
0.2g organo-bismuths 2010 and 2ml acetone adjustment viscosity, react 2.5h at 70 DEG C, and reaction terminates to determine NCO content, then cooled
To 0 DEG C, the triethylamine for adding 2.51g is neutralized, and neutralizes after 30min, deionized water is added under high speed shear, disperses 2min,
The acetone in 15g polyetheramine (molecular weight is 2000), vacuum distillation removing system is then slowly added into, that is, obtains aqueous poly- ammonia
Ester resin sample 3.
Embodiment 4
80g polyoxypropylene polyol (molecular weight is 4000) is dehydrated 1h at 105 DEG C, 50 DEG C are then cooled to, plus
Enter 15g XDI, be warming up to 90 DEG C of insulation reactions 3 hours, determine NCO content within two hours, reach reason
By being cooled to 50 DEG C after value, then add 2.3g dimethylolpropionic acids, 1.5g ethylene glycol and react 2h at 80 DEG C, be cooled to 50
DEG C, 0.2g organo-bismuth Coscat83 and 2ml acetone adjustment viscosity are then added, 2.5h is reacted at 70 DEG C, reaction terminates to determine
NCO content, is then cooled to 0 DEG C, and the triethylamine for adding 2.32g is neutralized, and neutralizes after 30min, adds and goes under high speed shear
Ionized water, disperses 2min, is then slowly added into third in 18g polyetheramine (molecular weight is 2000), vacuum distillation removing system
Ketone, that is, obtain waterborne polyurethane resin sample 4.
Embodiment 5
83g polysiloxane polyhydric alcohol (molecular weight is 3000) is dehydrated 1h at 105 DEG C, 50 DEG C, addition are then cooled to
15g Methylcyclohexyl diisocyanate, is warming up to 90 DEG C of insulation reactions 3 hours, determines NCO content within two hours, reaches theory
50 DEG C are cooled to after value, 2.5g dimethylolpropionic acids, 1.6g butanediols is then added and reacts 2h at 80 DEG C, be cooled to 50 DEG C,
Then 0.2g organo-bismuth Coscat83 and 3ml acetone adjustment viscosity are added, 3h is reacted at 70 DEG C, reaction terminates measure NCO and contained
Amount, is then cooled to 0 DEG C, and the triethylamine for adding 2.32g is neutralized, and neutralizes after 30min, deionization is added under high speed shear
Water, disperses 2min, is then slowly added into the acetone in 14g polyetheramine (molecular weight is 2000), vacuum distillation removing system, i.e.,
Obtain waterborne polyurethane resin sample 5.
Embodiment 6
Wet processing is respectively adopted in the acquisition waterborne polyurethane resin sample of embodiment 1 to 5 and prepares aqueous clothing leather bass.
The wet processing comprises the following steps：100 parts of above-mentioned aqueous polyurethanes are added 0.5 part under 700 revs/min of high speed shear
Wetting agent, 0.5 portion of filling powder, 1.2 portions of foaming agents, 0.3 portion of foam stabilizer, foam to 1.8 times of original volume, viscosity, which is made, is
15000mpas-18000mpas foamed slurry；Base fabric is plated, is then applied in base fabric and is covered with foamed slurry, then will be applied
The base fabric for covering foamed slurry is condensed by mass concentration in coagulating basin for 3% acetic acid aqueous solution, breaks aqueous polyurethane
Breast simultaneously forms porous packing with filling powder, is then cleaned by rinsing bowl, 2.5h is dried in the baking oven for being subsequently placed in 110 DEG C,
Obtain aqueous clothing leather bass sample.
Test result
According to light industry standard QB/T2958-2008《Clothes Synthetic Leather》To what is prepared by embodiment 1 to 5
Aqueous clothing leather bass sample progress performance test prepared by waterborne polyurethane resin is obtained by embodiment 1 to 5.
Table 1 is obtained the performance detection knot of aqueous clothing leather bass sample prepared by waterborne polyurethane resin by embodiment 1 to 5
Really
Table 1 is the performance detection that aqueous clothing leather bass sample prepared by waterborne polyurethane resin is obtained by embodiment 1 to 5
As a result, it is as shown in the table, and the aqueous polyurethane coating that embodiment 1-5 is prepared is soft, weatherability is strong；And peel off strong
Degree is high, and normal temperature folding strength is high.
In summary, the present invention is using the larger ehter bond macromolecular polyol of molecular weight so that waterborne polyurethane resin is gathered around
There are relatively low modulus and soft feel；The amine chain extender that the present invention is used, for polyetheramine, is polyethers on the main chain of polyetheramine
Structure, compared with other amine chain extenders, softness is many in feel, and polyetheramine molecular weight is larger, in the amino of demand same substance amount
In the case of, its quality is 5-80 times of other amine chain extenders, substantially increases the solid content of waterborne polyurethane resin, Jin Erti
The high richness of waterborne polyurethane resin.So, the present invention effectively overcomes various shortcoming of the prior art and has height
Industrial utilization.
The above, only presently preferred embodiments of the present invention, it is not any to the present invention in form and substantial limitation,
It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, can also make
Some improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the Equivalent embodiments of the present invention；Meanwhile, all substantial technologicals pair according to the present invention
The variation, modification and evolution for any equivalent variations that above-described embodiment is made, still fall within the scope of technical scheme
It is interior.
Claims (10)
1. a kind of waterborne polyurethane resin, it is characterised in that：Including following raw material components and parts by weight：
2. waterborne polyurethane resin as claimed in claim 1, it is characterised in that：The macromolecular polyol includes poly- tetrahydrochysene furan
Mutter in ethoxylated polyhydric alcohol, polyethylene oxide polyol, polyoxypropylene polyol, polyesterether polyols and polysiloxane polyhydric alcohol
Any one or more.
3. waterborne polyurethane resin as claimed in claim 1 or 2, it is characterised in that：The molecular weight of the macromolecular polyol
For 2500-4500.
4. waterborne polyurethane resin as claimed in claim 1, it is characterised in that：The isocyanates includes toluene diisocynate
Ester, IPDI, methyl diphenylene diisocyanate, hexamethylene diisocyanate, the isocyanide of phenylenedimethylidyne two
Acid esters, naphthalene -1,5- diisocyanate polymethylene multi-phenenyl isocyanate, tetramethylxylylene diisocyanate, methyl
Any one or more in cyclohexyl diisocyanate, dicyclohexyl methyl hydride diisocyanate.
5. waterborne polyurethane resin as claimed in claim 1, it is characterised in that：The hydrophilic chain extender includes dihydroxymethyl third
Acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and dihydroxymethyl octanoic acid in any one or more；
And/or, the small molecule alcohol chain extender include ethylene glycol, 2- methyl isophthalic acids, ammediol, diglycol, Isosorbide-5-Nitrae-
Butanediol, 2,3- butanediols, 1,6-HD, neopentyl glycol, diethylene glycol (DEG), glycerine, sorbierite, trimethylolpropane, dihydroxy first
Any one or more in butylcyclohexane.
6. waterborne polyurethane resin as claimed in claim 1, it is characterised in that：The amine chain extender is polyetheramine.
7. waterborne polyurethane resin as claimed in claim 1, it is characterised in that：The catalyst elects organic bismuth catalyst as.
8. a kind of method for preparing the waterborne polyurethane resin as described in claim 1 to 7 is any, it is characterised in that：Including with
Lower step：The polyalcohol and the polyisocyanates react 2~3h at 85~95 DEG C；Add the hydrophilic chain extender and
The small molecule alcohol chain extender reacts 1.5~2.5h at 75~85 DEG C；Then the catalyst is added, at 65~75 DEG C
2~3h is reacted, -5~5 DEG C is cooled to and adds the salt forming agent neutralization；The amine chain extender is added after adding water, decompression is steamed
Evaporate, obtain waterborne polyurethane resin.
9. the preparation method of waterborne polyurethane resin as claimed in claim 8, it is characterised in that：Add the same of the catalyst
When add acetone.
10. purposes of the waterborne polyurethane resin in the wet processing of aqueous clothing leather bass as described in claim 1 to 7 is any.
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| CN107312155A (en) * | 2017-08-18 | 2017-11-03 | 江苏宝泽高分子材料股份有限公司 | It is a kind of soft without viscous aqueous polyurethane leather surface material and preparation method thereof |
| CN108164674A (en) * | 2017-12-29 | 2018-06-15 | 浙江华峰合成树脂有限公司 | The high bright resistance to tortuous polyurethane leather resin of solvent-free non yellowing and preparation method and application |
| CN109096466A (en) * | 2018-07-17 | 2018-12-28 | 合肥科天水性科技有限责任公司 | A kind of preparation method of biology base water polyurethane bass |
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| CN110117912A (en) * | 2019-04-08 | 2019-08-13 | 温州大学 | A kind of aqueous polyurethane for woven fabric bass |
| WO2019232704A1 (en) * | 2018-06-06 | 2019-12-12 | Dow Global Technologies Llc | Aqueous coating composition |
| CN110643013A (en) * | 2019-10-08 | 2020-01-03 | 浙江合力革业有限公司 | Novel synthetic leather material and preparation method thereof |
| CN110845698A (en) * | 2019-11-19 | 2020-02-28 | 合众（佛山）化工有限公司 | Polyether amine modified waterborne polyurethane resin and preparation method thereof |
| CN111138614A (en) * | 2019-12-19 | 2020-05-12 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion for low-modulus high-strength ultrathin polyurethane condom and preparation method thereof |
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| CN114349930A (en) * | 2022-01-17 | 2022-04-15 | 万华化学集团股份有限公司 | Waterborne polyurethane resin emulsion, preparation method and earphone cover leather |
| CN114907545A (en) * | 2022-06-06 | 2022-08-16 | 合肥科天水性科技有限责任公司 | High-solid-content waterborne polyurethane for super-soft synthetic leather dry-process mechanical foaming coating |
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| CN109608605A (en) * | 2017-12-19 | 2019-04-12 | 传化智联股份有限公司 | A kind of ion-non-ion aqueous polyurethane dispersion preparation |
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| CN110117912A (en) * | 2019-04-08 | 2019-08-13 | 温州大学 | A kind of aqueous polyurethane for woven fabric bass |
| CN110643013A (en) * | 2019-10-08 | 2020-01-03 | 浙江合力革业有限公司 | Novel synthetic leather material and preparation method thereof |
| CN110845698A (en) * | 2019-11-19 | 2020-02-28 | 合众（佛山）化工有限公司 | Polyether amine modified waterborne polyurethane resin and preparation method thereof |
| CN111138614A (en) * | 2019-12-19 | 2020-05-12 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion for low-modulus high-strength ultrathin polyurethane condom and preparation method thereof |
| CN114075322A (en) * | 2020-08-18 | 2022-02-22 | 上海名邦橡胶制品有限公司 | Waterborne polyurethane resin emulsion and preparation method thereof |
| CN113372530A (en) * | 2021-05-19 | 2021-09-10 | 万华化学集团股份有限公司 | Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base |
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| CN114349930A (en) * | 2022-01-17 | 2022-04-15 | 万华化学集团股份有限公司 | Waterborne polyurethane resin emulsion, preparation method and earphone cover leather |
| CN114349930B (en) * | 2022-01-17 | 2023-07-04 | 万华化学集团股份有限公司 | Aqueous polyurethane resin emulsion and preparation method thereof, and earphone sleeve leather |
| CN114907545A (en) * | 2022-06-06 | 2022-08-16 | 合肥科天水性科技有限责任公司 | High-solid-content waterborne polyurethane for super-soft synthetic leather dry-process mechanical foaming coating |
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