CN104262571B - A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin - Google Patents
A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin Download PDFInfo
- Publication number
- CN104262571B CN104262571B CN201410483653.XA CN201410483653A CN104262571B CN 104262571 B CN104262571 B CN 104262571B CN 201410483653 A CN201410483653 A CN 201410483653A CN 104262571 B CN104262571 B CN 104262571B
- Authority
- CN
- China
- Prior art keywords
- polyurethane resin
- waterborne polyurethane
- preparation
- acetone
- poly
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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
-
- 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
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
-
- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
-
- 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
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The present invention proposes a kind of preparation method of soft large arch dam waterborne polyurethane resin, and step is as follows：1) by after the polyester polyol containing at least one sodium group, polyols blend mixed dehydration on molecular backbone, reacted with aromatic diisocyanate, polyurethane prepolymer is made；2) polyurethane prepolymer for preparing step 1) adds small molecule dihydric alcohol, end-blocking；3) after acetone dilution, emulsification, amine chainextender reaction is added, polyurethane dispersing liquid is made；4) acetone in above-mentioned polyurethane dispersing liquid is removed, obtains waterborne polyurethane resin.The application preparation method applicability is wide, can prepare the soft waterborne polyurethane resin of various different performance requirements and purposes；The advantages that solid content of prepared waterborne polyurethane resin is high, film forming is soft flexible, low-temperature flexibility is good, cost-effective, can be widely applied to the soft coating or decoration in the fields such as weaving, leather, synthetic leather.
Description
Technical field
The invention belongs to waterborne polyurethane resin preparation field, more particularly, to large arch dam and soft or submissive
The preparation method of the good waterborne polyurethane resin of property.
Background technology
Polyurethane resin has a wide range of applications as a kind of high performance polymer material in various fields.Traditional is poly-
Urethane material is mainly solvent borne polyurethane, and containing substantial amounts of organic solvent, serious harm is caused to environment and human body.It is water-based
Polyurethane is free of using water as dissolving medium or contains organic solvent on a small quantity, the row of volatilizable organic matter (VOC) is greatly reduced
Put, and save the energy and resource.With countries in the world government and the pay attention to day by day among the people to environmental protection, the limitation to VOC emission
Also all the more stringent, it is an a development trend to replace solvent borne polyurethane with aqueous polyurethane, the adhesive of aqueous polyurethane, coating,
The fields such as coating, ink, prospect are very wide.
Due to technical elements, presently commercially available aqueous polyurethane solid content is relatively low (being usually no more than 40%), leads
Slow drying speed is caused, film forming is not plentiful, and increases cost of transportation, energy expenditure when increase is dry.
The research and development of high-solid content water-based polyurethane is important trend, in patent CN102206410B, is prepared
Method and step include prepolymerization reaction (preparing prepolymer), it is monomer modified, be neutralized into salt and emulsification chain extension, using carboxylic acid type
The method being combined with sulfonic acid type hydrophilic chain extender, isocyanate-monomer, system are used as using aliphatic and alicyclic diisocyanate
It can be used for synthetic leather field for waterborne polyurethane resin of the solid content in 50-60%, the resin；Because aliphatic isocyanates
Higher price, while the materials such as organosilicon are added, high expensive, is unfavorable for large-scale industrialization promotion.
In patent CN103360563, preparation method step include prepare polyurethane prepolymer, mixing polyurethane from aggressiveness,
Lotion is made after chain extension.Using ethylenediamine base ethyl sulfonic acid sodium as hydrophilic chain extender, isophorone diisocyanate (IPDI) and
Hexamethylene diisocyanate (HDI) is used as isocyanate-monomer, prepares the waterborne polyurethane resin that solid content reaches 50%, system
Standby polyurethane prepolymer will also polymerize by the interlinkage of two, which equally exists high expensive, be unfavorable for pushing away on a large scale
Extensively.
In patent CN103613730A, the also preparation including prepolymer and chain extension in preparation method, also using second
Two amido ethyl sulfonic acid sodium obtain receiving for stabilization as hydrophilic chain extender, isophorone diisocyanate as isocyanate-monomer
The silica modified large arch dam waterborne polyurethane resin of rice.Since ethylenediamine base ethyl sulfonic acid sodium is the amine containing two high activities
Base hydrophilic chain extender, and the rapid reaction of isocyanates, generally require and add reaction at a lower temperature, and need reacting
Later stage add, therefore can only generally use the relatively low isocyanate-monomer (such as IPDI, HDI) of activity, and both monomers
Often higher price, greatly improved the cost of large arch dam waterborne polyurethane resin.
The content of the invention
The present invention proposes a kind of preparation method of large arch dam waterborne polyurethane resin, and manufacturing cost is relatively low, can make
Standby various different performances requirement and the waterborne polyurethane resin of purposes, using containing at least one sodium group on molecular backbone
Polyester polyol as hydrophilic chain extender, be added in reaction system initial stage, be more uniformly reacted to poly- in polymerisation
In urethane strand.
The technical solution adopted by the present invention is as follows：
A kind of preparation method for soft large arch dam waterborne polyurethane resin that one aspect of the present invention provides, step are as follows：
1) polyester polyol, the polyols blend mixed dehydration of at least one sodium group will be contained on molecular backbone
Afterwards, reacted with aromatic diisocyanate, polyurethane prepolymer is made；
2) polyurethane prepolymer for preparing step 1) adds small molecule dihydric alcohol, end-blocking；
3) after acetone dilution, emulsification, amine chainextender reaction is added, polyurethane dispersing liquid is made；
4) acetone in above-mentioned polyurethane dispersing liquid is removed, obtains waterborne polyurethane resin.
Above-mentioned preparation method, it is further preferred that comprising the following steps that：
1) under nitrogen protection, by the polyester polyol for containing at least one sodium group on molecular backbone and mix polynary
Alcohol heating is melted and stirred, when decompression dehydration 1-2 is small under 110-130 DEG C, vacuum 0.09-0.1MPa；It is cooled to 50-60
DEG C, add acetone adjust viscosity, be stirring evenly and then adding into aromatic diisocyanate, be warming up to 70-90 DEG C and react 1-3 it is small when
Afterwards, polyurethane prepolymer is made；
2) polyurethane prepolymer prepared in step 1) adds small molecule dihydric alcohol end-blocking, reacts to NCO theoretical values；
3) acetone dilution step 2) prepared by reactant, under high shear, add deionized water emulsified
1-2min, after emulsification, stirs lower addition amine chainextender, and continues to stir 5-10min, obtains polyurethane dispersing liquid；
4) polyurethane dispersing liquid prepared by step 3) is heated to 45-55 DEG C, in the above-mentioned polyurethane dispersing liquid of removed under reduced pressure
Acetone, obtains waterborne polyurethane resin.
In above-mentioned preparation method, it is further preferred that containing at least one sodium group on the molecular backbone
Polyester polyol be the molecular weight by sulfonation be 800-3000 poly- fumaric acid-adipic acid-ethylene glycol, poly- fumaric acid-oneself two
Acid-diglycol ester polyol or poly- fumaric acid-adipic acid-ethylene glycol-diglycol polyalcohol；
The polyols blend is that the polyester polyol that molecular weight is 500-3000 or polyether polyol or both are mixed
Compound；
The small molecule dihydric alcohol is selected from ethylene glycol, 1,3-PD, 1,2-PD, 1,4-butanediol, 1,3- fourths
Glycol, diglycol, one or more of mixtures of 1,6- hexylene glycols；
The aromatic diisocyanate is toluene di-isocyanate(TDI)；
The amine chainextender is selected from ethylenediamine, hexamethylene diamine, piperazine, 2,5- lupetazins, isophorone diamine, 4-
One or more of mixtures in 4 '-diaminocyclohexyl methane, Isosorbide-5-Nitrae-diaminocyclohexane, hydrazine, adipic dihydrazide.
It is further preferred that the polyester polyol containing at least one sodium group is process on the molecular backbone
The molecular weight of sulfonation is poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester polyol of 1000-2000；
The polyols blend is polyethylene glycol adipate glycol, the polyneopentyl glycol adipate of 1000-2000
Glycol, polyadipate -1,4-butanediol esterdiol, polyadipate -1,6- hexylene glycol esterdiol, poly- ε-caprolactone diol, poly- carbon
Acid esters glycol or polytetrahydrofuran ether glycol；
The small molecule dihydric alcohol is selected from ethylene glycol, 1,4-butanediol, 1,6- hexylene glycols；
The amine chainextender is selected from ethylenediamine, hexamethylene diamine, piperazine, 2,5- lupetazins, isophorone diamine.
It is further preferred that the polyester polyol containing at least one sodium group is process on the molecular backbone
The molecular weight of sodium hydrogensulfite sulfonation is that poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester of 1000-2000 is polynary
Alcohol；
The polyols blend be molecular weight be 1000-2000 polyethylene glycol adipate glycol, polyadipate it is new
Pentadiol ester glycol, polyadipate -1,4-butanediol esterdiol；
The small molecule dihydric alcohol is 1,4-butanediol；
The amine chainextender is selected from ethylenediamine, piperazine, 2,5- lupetazins, isophorone diamine.
It is further preferred that the polyester polyol containing at least one sodium group is process on the molecular backbone
The molecular weight of sodium hydrogensulfite sulfonation is 1000-2000, poly- fumaric acid-adipic acid-second two of the acid number less than 0.3mgKOH/g
Alcohol-diglycol ester dihydric alcohol；The amine chainextender is isophorone diamine.
Wherein, the above-mentioned molecular weight by sulfonation is 800-3000 poly- fumaric acid-adipic acid-ethylene glycol, poly- rich horse
Acid-adipic acid-diglycol ester polyol or poly- fumaric acid-adipic acid-ethylene glycol-diglycol polyalcohol or
Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester that molecular weight preferable through sulfonation is 1000-2000 is polynary
Alcohol, contains at least one sodium group on main chain, as by sulfonation, contain at least one sodium sulfonate group on molecular backbone
Roll into a ball, molecular weight is poly- fumaric acid-adipic acid-ethylene glycol, the poly- fumaric acid-adipic acid-diglycol ester of 800-3000
Polyalcohol or poly- fumaric acid-adipic acid-ethylene glycol-diglycol polyalcohol or preferable through sulfonation, molecule master
Poly- fumaric acid-adipic acid that contain at least one sodium group on chain, that molecular weight the is 1000-2000-contracting of ethylene glycol-one two
Glycol ester polyalcohol.
Above-mentioned polyols blend, small molecule dihydric alcohol and amine chainextender can use the arbitrary proportion of the compound to mix
Compound, because the compound is in the polymerization, the function of enforcement is close.
In addition, in above-mentioned reaction, the percentage by weight of each reaction raw materials is as follows：
Polyester polyol 5~20% containing at least one sodium group, the mixing on the molecular backbone
It is polyalcohol 70~80%, the aromatic diisocyanate 10~22%, the small molecule dihydric alcohol 2~4%, described
Amine chainextender 1~2%；
Acetone dosage described in step 3) is the 80~100% of reactant weight prepared in step 2)；Described
The water content of acetone is less than 3000ppm.Wherein, acetone adjusts the performances such as viscosity as solvent.
It is further preferred that contain the weight of the polyester polyol of at least one sodium group on the molecular backbone
Percentage is 10~15%.
In above-mentioned preparation method, NCO theoretical values are less than or equal to 1.1%~1.2%.
On the other hand, in the application, the soft large arch dam waterborne polyurethane resin of above method preparation is applied to spin
Knit, the coating of leather or synthetic leather；Further, the large arch dam waterborne polyurethane resin that prepared by the above method is applied to leather side
Oil or synthetic leather wet method foamed slurry.
Sulfonating reaction, one kind introduce sulfonic group (- SO3H) or its corresponding salt or sulfonic acid halide into organic compound molecule
Any chemical process of base, containing at least containing a sulfonic group in the molecular backbone of the organic compound after sulfonating reaction.
Contain the polyester polyol of at least one sodium group on molecular backbone, add the surface-active of polyalcohol,
Sulfonic group wherein on molecule can further be substituted by other groups, and activity is higher, in prepolymer reaction, contain on molecular backbone
There are polyester polyol, other polyester polyol (being different from the former) and the aromatic diisocyanate polymerization of sodium group instead
At once, the hydroxyl of NCO group and polyester polyol carries out reaction and forms main polymer chain, and sulfonic acid group can be by hydroxyl, amino etc.
Group substitutes, and is conducive to the formation of prepolymer macromolecular or net structure.Aromatic diisocyanate such as toluene di-isocyanate(TDI),
When preparing aqueous dispersion, many precipitations are also easy to produce, have caused stability to decline, using containing sulphur on the molecular backbone of high activity
The polyester polyol of sour sodium group, the polyurethane prepolymer of formation have good dispersiveness and storage stability；Especially adopt
With toluene di-isocyanate(TDI), there is phenyl ring, the molecule for forming polymer has more outstanding stability；And aromatic series two is different
The price of cyanate is relatively low, and manufacturing cost is relatively low.
In addition, poly- fumaric acid-adipic acid-ethylene glycol is prepared by the polymerization of fumaric acid, adipic acid and ethylene glycol；Poly- richness
Horse acid-adipic acid-diglycol ester polyol is prepared by fumaric acid, adipic acid, diglycol；Poly- richness horse
Acid-adipic acid-ethylene glycol-diglycol polyalcohol or poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester two
First alcohol is prepared by fumaric acid, adipic acid, ethylene glycol and diglycol；Wherein fumaric acid, also known as butene dioic acid,
It is all double carboxylic acids with adipic acid, ethylene glycol and diglycol are all dihydric alcohol, are referred to polyethylene glycol adipate
The preparation methods such as dihydric alcohol.
Amine chainextender contains the compound of double amino using ethylenediamine, hexamethylene diamine, piperazine etc., it is further preferred that using
The organic heterocyclic molecules such as isophorone diamine, piperazine or derivatives thereof, have the formula design freedom of higher, in polymer
The presence of heterocycle structure makes waterborne polyurethane resin that there is good intensity and hardness to exist, and strengthens quick-dry type, while have colourity
Stability and morphology, storage stability.
In preparation process, before the polyester polyol containing sodium group and other polyols blends can be pre-added to
In phase reaction, then it is directly added into diisocyanate and carries out polymerisation, form polyurethane prepolymer, preparation method is relatively simple
It is single；Subsequent end-blocking and add in amine chainextender curing reaction, it is not necessary to which substantial amounts of acetone participates in reaction, relatively current preparation side
The use of acetone in method, acetone dosage is less in the application, shortens acetone recovery time.
The application preparation method applicability is wide, can prepare the soft aqueous polyurethane of various different performance requirements and purposes
Resin；The solid content of prepared waterborne polyurethane resin is high, film forming softness is flexible, low-temperature flexibility is good, cost performance is high etc.
Advantage, can be widely applied to the soft coating or decoration in the fields such as weaving, leather, synthetic leather.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's all other embodiments obtained without creative efforts, belong to this hair
The scope of bright protection.
A kind of preparation method of soft large arch dam waterborne polyurethane resin of embodiment 1
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
Poly- fumaric acid-the adipic acid-one for containing at least one sodium group on 200g main chains, molecular weight is 2000 is contracted
Diethylene glycol ester polyol and polyadipate -1,4-butanediol esterdiol that 1400g molecular weight is 2000 are put into reaction kettle,
Heating heating is melted and stirred evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 60
DEG C, 200g acetone is added, is stirring evenly and then adding into 260g toluene di-isocyanate(TDI)s (TDI), when being warming up to 80 DEG C and small reaction 2,
Obtain polyurethane prepolymer.
Then, add 40g ethylene glycol the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, reaction knot
Beam.It is added drop-wise to 1900g acetone in reactant and is diluted and cools down.Acetone is added dropwise, and under high shear, adds
1930g deionized waters carry out emulsification 1-2min.
After emulsification, 26g isophorone diamine is added, and continues to stir 5-10min, obtains polyurethane dispersing liquid.Will
Dispersion liquid is heated to 50 DEG C, and the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of soft large arch dam waterborne polyurethane resin of embodiment 2
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By the poly- fumaric acid-adipic acid-diglycol ester polyol and 1400g molecules that 220g molecular weight is 2000
Measure the polyadipate for 2000-neopentyl glycol esterdiol to put into reaction kettle, heating heating is melted and stirred evenly.120
DEG C, when decompression dehydration 1 is small under vacuum 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, adds after stirring evenly
Enter 278g toluene di-isocyanate(TDI)s (TDI), when being warming up to 80 DEG C and small reaction 2, obtain polyurethane prepolymer.
Then, add 60g 1,6- hexylene glycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.2%, instead
It should terminate.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1980g deionized waters and carry out emulsification 1-2min.
After emulsification, 29.5g isophorone diamine is added, and continues to stir 5-10min, obtains polyurethane dispersing liquid.
Dispersion liquid is heated to 50 DEG C, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 3
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By poly- fumaric acid-adipic acid-second two that 300g main chains contain at least one sodium group, molecular weight is 3000
Alcohol-diglycol polyalcohol and the polytetrahydrofuran ether glycol that 1500g molecular weight is 2000 are put into reaction kettle, are heated up
Heating is melted and stirred evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C,
200g acetone is added, is stirring evenly and then adding into 280.5g toluene di-isocyanate(TDI)s (TDI), when being warming up to 80 DEG C and small reaction 2, is obtained
To polyurethane prepolymer.
Then, add 30g ethylene glycol the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, reaction knot
Beam.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, and under high shear, adds
1980g deionized waters carry out emulsification 1-2min.
After emulsification, 10g ethylenediamines are added, and continue to stir 5-10min, obtain polyurethane dispersing liquid.By dispersion liquid
50 DEG C are heated to, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 4
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By poly- fumaric acid-adipic acid-ethylene glycol that 100g main chains contain at least one sodium group, molecular weight is 800
Put into 1600g molecular weight for 500 polyethylene glycol adipate glycol in reaction kettle, heating heating, which is melted, simultaneously stirs
It is even.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds 200g acetone, stirring
200g toluene di-isocyanate(TDI)s (TDI) are added after uniformly, when being warming up to 70 DEG C and small reaction 2, obtain polyurethane prepolymer.
Then, add 60g 1,3-PDs the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, instead
It should terminate.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1980g deionized waters and carry out emulsification 1-2min.
After emulsification, 40g 4-4 '-diaminocyclohexyl methane is added, and continues to stir 5-10min, obtains polyurethane
Dispersion liquid.Dispersion liquid is heated to 45 DEG C, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains aqueous polyurethane tree
Fat.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 5
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By poly- fumaric acid-adipic acid-second two that 100g main chains contain at least one sodium group, molecular weight is 1000
Alcohol-diglycol ester polyol and polyadipate -1,4-butanediol esterdiol that 1400g molecular weight is 1500 are put into instead
Answer in kettle, heating heating is melted and stirred evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates,
60 DEG C are cooled to, 200g acetone is added, is stirring evenly and then adding into 440g toluene di-isocyanate(TDI)s (TDI), is warming up to 90 DEG C simultaneously instead
Answer 2 it is small when, obtain polyurethane prepolymer.
Then, add 40g ethylene glycol the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, reaction knot
Beam.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, and under high shear, adds
1980g deionized waters carry out emulsification 1-2min.
After emulsification, 20g ethylenediamines are added, and continue to stir 5-10min, obtain polyurethane dispersing liquid.By dispersion liquid
55 DEG C are heated to, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 6
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By poly- fumaric acid-adipic acid-second two that 200g main chains contain at least one sodium group, molecular weight is 2000
Alcohol-diglycol ester polyol and the poly-epsilon-caprolactone glycol that 1500g molecular weight is 2000 are put into reaction kettle, are heated up
Heating is melted and stirred evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds
Enter 200g acetone, be stirring evenly and then adding into 200g toluene di-isocyanate(TDI)s (TDI), when being warming up to 70 DEG C and small reaction 2, gathered
Urethane prepolymer.
Then, add 70g diglycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%,
Reaction terminates.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, in high shear
Under, add 1980g deionized waters and carry out emulsification 1-2min.
After emulsification, 30g piperazines are added, and continue to stir 5-10min, obtain polyurethane dispersing liquid.By dispersion liquid plus
For heat to 45 DEG C, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 7
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
By poly- fumaric acid-adipic acid-second two that 200g main chains contain at least one sodium group, molecular weight is 2000
Alcohol-diglycol ester polyol and the polycarbonate glycol that 1500g molecular weight is 2000 are put into reaction kettle, and heating adds
Heat fusing simultaneously stirs evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds
200g acetone, is stirring evenly and then adding into 200g toluene di-isocyanate(TDI)s (TDI), when being warming up to 70 DEG C and small reaction 2, obtains poly- ammonia
Ester prepolymer.
Then, add 70g diglycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%,
Reaction terminates.It is added drop-wise to 2000g acetone in reactant and is diluted and cools down.Acetone is added dropwise, in high shear
Under, add 1980g deionized waters and carry out emulsification 1-2min.
After emulsification, 30g 2,5- lupetazins are added, and continues to stir 5-10min, obtains polyurethane dispersing liquid.
Dispersion liquid is heated to 45 DEG C, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 8
With embodiment 7 difference lies in：Using piperazine and 2, the mixture of 5- lupetazins, mixed weight ratio is 1:
2；Using poly-epsilon-caprolactone glycol and polycarbonate glycol mixture, mixed weight ratio is 1:3；Using 1,3-PD, 1,
The mixture of 2- propane diols, mixed weight ratio are 1:3.
A kind of preparation method of soft large arch dam waterborne polyurethane resin of embodiment 9
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
It is by sodium hydrogensulfite sulphur by the polyester polyol for containing at least one sodium group on 210g molecular backbones
The molecular weight of change be 2000, acid number be less than 0.3mgKOH/g poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester
Dihydric alcohol and polyadipate -1,4-butanediol esterdiol that 1400g molecular weight is 2000 are put into reaction kettle, and heating heating is molten
Change and stir evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g
Acetone, is stirring evenly and then adding into 260g toluene di-isocyanate(TDI)s (TDI), when being warming up to 80 DEG C and small reaction 2, obtains polyurethane
Prepolymer.
Then, add 40g 1,4-butanediol the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, instead
It should terminate.It is added drop-wise to 1900g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1930g deionized waters and carry out emulsification 1-2min.
After emulsification, 26g isophorone diamine is added, and continues to stir 5-10min, obtains polyurethane dispersing liquid.Will
Dispersion liquid is heated to 50 DEG C, and the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 10
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
It is by sodium hydrogensulfite sulphur by the polyester polyol for containing at least one sodium group on 210g molecular backbones
The molecular weight of change be 2000, acid number be less than 0.3mgKOH/g poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester
Dihydric alcohol and polytetrahydrofuran ether glycol and mixture (the mixed weight ratio of polycarbonate glycol that 1400g molecular weight is 1500
Example 1:2) put into reaction kettle, heating heating is melted and stirred evenly.Decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa
When.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, is stirring evenly and then adding into 260g toluene di-isocyanate(TDI)s (TDI), rises
Temperature to 80 DEG C and react 2 it is small when, obtain polyurethane prepolymer.
Then, add 40g 1,6- hexylene glycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, instead
It should terminate.It is added drop-wise to 1900g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1930g deionized waters and carry out emulsification 1-2min.
After emulsification, 26g isophorone diamine is added, and continues to stir 5-10min, obtains polyurethane dispersing liquid.Will
Dispersion liquid is heated to 50 DEG C, and the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 11
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
At least one sodium group will be contained on 200g molecular backbones, the molecular weight by sodium hydrogensulfite sulfonation is
2000, acid number be less than 0.3mgKOH/g poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester dihydric alcohol and 1400g
Molecular weight is that 1500 polytetrahydrofuran ether glycol and the mixture of polycarbonate glycol are put into reaction kettle, and heating heating is molten
Change and stir evenly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 55 DEG C, adds 200g
Acetone, adds 300g toluene di-isocyanate(TDI)s (TDI) after stirring evenly, when being warming up to 80 DEG C and small reaction 2, obtain polyurethane prepolymer
Thing.
Then, add 60g 1,6- hexylene glycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, instead
It should terminate.It is added drop-wise to 1900g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1930g deionized waters and carry out emulsification 1-2min.
After emulsification, 40g hydrazines are added, and continue to stir 5-10min, obtain polyurethane dispersing liquid.Dispersion liquid is heated
To 50 DEG C, the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 12
The preparation method of large arch dam waterborne polyurethane resin, step are as follows：
At least one sodium group will be contained on 300g molecular backbones, molecular weight passes through sodium hydrogensulfite sulfonation for 1600
Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester dihydric alcohol and 1400g molecular weight are 1500 polytetrahydrofuran ether
(mixed weight ratio is 1 for glycol and the mixture of polycarbonate glycol:5) put into reaction kettle, heating heating is melted and stirred
Mix uniformly.When decompression dehydration 1 is small under 120 DEG C, vacuum 0.1MPa.Dehydration terminates, and is cooled to 55 DEG C, adds 200g acetone,
Add 200g toluene di-isocyanate(TDI)s (TDI) after stirring evenly, when being warming up to 80 DEG C and small reaction 2, obtain polyurethane prepolymer.
Then, add 60g 1,6- hexylene glycols the reaction was continued 2 it is small when, if measuring NCO% less than or equal to 1.1%, instead
It should terminate.It is added drop-wise to 1900g acetone in reactant and is diluted and cools down.Acetone is added dropwise, under high shear,
Add 1930g deionized waters and carry out emulsification 1-2min.
After emulsification, 40g adipic dihydrazides are added, and continue to stir 5-10min, obtain polyurethane dispersing liquid.Will
Dispersion liquid is heated to 50 DEG C, and the acetone under -0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
A kind of preparation method of large arch dam waterborne polyurethane resin of embodiment 13
With embodiment 12 difference lies in：Using polyadipate -1,4-butanediol esterdiol, polyadipate -1,6- hexylene glycol
(mixed weight ratio is 1 to the mixture of esterdiol:2) polyols blend is used as, using adipic dihydrazide and Isosorbide-5-Nitrae-diaminourea
(mixed weight ratio is 1 to the mixture of hexamethylene:4) it is used as amine chainextender；Blocked using 1,4-butanediol.
The solid content height of the waterborne polyurethane resin prepared in above-described embodiment can reach 50%, soft and soft, bullet
Property is preferable.The main performance that waterborne polyurethane resin is prepared in embodiment 1-3 is as shown in table 1：
Table 1：
The main performance of the waterborne polyurethane resin prepared in embodiment 9-11 is as shown in table 2：
Table 2：
Wherein, milky white band blue light is presented in the waterborne polyurethane resin appearance that prepared by embodiment 1-7 embodiments 8~13, admittedly contain
Amount is average more than 50%, and storage cycle is longer；Resin can also show outstanding performance, explanation in the mechanical property of film
The hard section and soft segment of the waterborne polyurethane resin of preparation reach balance, can both keep excellent softness, while have excellent
Elegant mechanical strength performance.
Waterborne polyurethane resin prepared by above-described embodiment is applied to the coating of weaving, leather or synthetic leather or applied to skin
Side oil or synthetic leather wet method foamed slurry are removed from office, using the preparation method of this area routine, raw material includes prepared by above-described embodiment
The materials such as waterborne polyurethane resin, colorant, defoamer, preservative, levelling agent.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of preparation method of soft large arch dam waterborne polyurethane resin, it is characterized in that, step is as follows：
1) under nitrogen protection, the polyester polyol and polyols blend that contain at least one sodium group on molecular backbone are added
Heat fusing simultaneously stirs, when decompression dehydration 1-2 is small under 110-130 DEG C, vacuum 0.09-0.1MPa；50-60 DEG C is cooled to, is added
Enter acetone adjust viscosity, be stirring evenly and then adding into aromatic diisocyanate, be warming up to 70-90 DEG C and react 1-3 it is small when after, system
Obtain polyurethane prepolymer；
2) polyurethane prepolymer prepared in step 1) adds small molecule dihydric alcohol end-blocking, reacts to NCO theoretical values；
3) acetone dilution step 2) prepared by reactant, under high shear, add deionized water carry out emulsification 1-
2min, after emulsification, stirs lower addition amine chainextender, and continues to stir 5-10min, obtains polyurethane dispersing liquid；
4) polyurethane dispersing liquid prepared by step 3) is heated to 45-55 DEG C, the acetone in the above-mentioned polyurethane dispersing liquid of removed under reduced pressure,
Obtain waterborne polyurethane resin；
The polyols blend is the polyester polyol that molecular weight is 500-3000 or polyether polyol or both mixtures；
The polyester polyol containing at least one sodium group is to be by the molecular weight of sulfonation on the molecular backbone
Poly- fumaric acid-adipic acid-ethylene glycol, poly- fumaric acid-adipic acid-diglycol ester polyol or the poly- rich horse of 800-3000
Acid-adipic acid-ethylene glycol-diglycol polyalcohol.
2. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 1, it is characterized in that：
The small molecule dihydric alcohol be selected from ethylene glycol, 1,3-PD, 1,2-PD, 1,4-butanediol, 1,3-BDO,
One or more of mixtures of diglycol, 1,6- hexylene glycols；
The aromatic diisocyanate is toluene di-isocyanate(TDI)；
The amine chainextender is selected from ethylenediamine, hexamethylene diamine, piperazine, 2,5- lupetazins, isophorone diamine, 4-4 '-two
One or more of mixtures in aminocyclohexylmethane, Isosorbide-5-Nitrae-diaminocyclohexane, hydrazine, adipic dihydrazide.
3. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 2, it is characterized in that：It is described
Molecular backbone on the polyester polyol containing at least one sodium group be that molecular weight by sulfonation is 1000-2000's
Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester polyol；
The polyols blend be the polyethylene glycol adipate glycol of 1000-2000, polyneopentyl glycol adipate glycol,
Polyadipate -1,4-butanediol esterdiol, polyadipate -1,6- hexylene glycol esterdiol, poly-epsilon-caprolactone glycol, makrolon two
Alcohol or polytetrahydrofuran ether glycol；
The small molecule dihydric alcohol is selected from ethylene glycol, 1,4-butanediol, 1,6- hexylene glycols；
The amine chainextender is selected from ethylenediamine, hexamethylene diamine, piperazine, 2,5- lupetazins, isophorone diamine.
4. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 3, it is characterized in that：It is described
Molecular backbone on the polyester polyol containing at least one sodium group be that molecular weight by sodium hydrogensulfite sulfonation is
Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester polyol of 1000-2000；
The polyols blend be molecular weight be 1000-2000 polyethylene glycol adipate glycol, polyadipate new penta 2
Alcohol esterdiol, polyadipate -1,4-butanediol esterdiol；
The small molecule dihydric alcohol is 1,4-butanediol；
The amine chainextender is selected from ethylenediamine, piperazine, 2,5- lupetazins, isophorone diamine.
5. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 4, it is characterized in that：It is described
Molecular backbone on the polyester polyol containing at least one sodium group be that molecular weight by sodium hydrogensulfite sulfonation is
Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester dihydric alcohol of 1000-2000；The amine chainextender is different Fo Er
Ketone diamines；Poly- fumaric acid-adipic acid-ethylene glycol-diglycol ester dihydric alcohol the acid number is less than 0.3mgKOH/g.
6. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 1, it is characterized in that, it is each anti-
Answer the percentage by weight of raw material as follows：
The polyester polyol 5~20% containing at least one sodium group, the mixing are polynary on the molecular backbone
Alcohol 70~80%, the aromatic diisocyanate 10~22%, the small molecule dihydric alcohol 2~4%, the amine expand
Chain agent 1~2%；
Acetone dosage described in step 3) is the 80~100% of reactant weight prepared in step 2)；The acetone
Water content be less than 3000ppm.
7. a kind of preparation method of soft large arch dam waterborne polyurethane resin as claimed in claim 6, it is characterized in that：It is described
Molecular backbone on containing at least one sodium group polyester polyol percentage by weight be 10~15%.
8. soft large arch dam waterborne polyurethane resin prepared by claim any one of 1-7 be applied to weaving, leather and
The coating of synthetic leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410483653.XA CN104262571B (en) | 2014-09-19 | 2014-09-19 | A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410483653.XA CN104262571B (en) | 2014-09-19 | 2014-09-19 | A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104262571A CN104262571A (en) | 2015-01-07 |
| CN104262571B true CN104262571B (en) | 2018-05-15 |
Family
ID=52154175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410483653.XA Active CN104262571B (en) | 2014-09-19 | 2014-09-19 | A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262571B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693403B (en) * | 2015-03-17 | 2019-05-10 | 浙江深蓝新材料科技有限公司 | A kind of use for synthetic leather colour polyurethane resin and preparation method thereof |
| CN105330812B (en) * | 2015-12-03 | 2017-12-01 | 上海蓝欧化工科技有限公司 | A kind of low gloss aqueous polyurethane with skin sense effect and preparation method thereof |
| CN107057028A (en) * | 2017-02-20 | 2017-08-18 | 深圳凯奇化工有限公司 | A kind of water nano height covers 3D printing coating and preparation method thereof |
| CN108546324A (en) * | 2018-05-17 | 2018-09-18 | 厦门安踏体育用品有限公司 | A kind of non-Newtonian fluid material and intelligent Anti-knocking textile |
| CN109206588A (en) * | 2018-08-23 | 2019-01-15 | 洛阳盛嘉新材料有限公司 | High solid amount contains big partial size from delustring aqueous polyurethane and preparation method thereof |
| KR20220016638A (en) * | 2020-08-03 | 2022-02-10 | 주식회사 동성케미컬 | Water-disperson polyurethane-urea resin composition for synthetic leather and manufacturing method thereof |
| CN113279265A (en) * | 2021-02-05 | 2021-08-20 | 山东天庆科技发展有限公司 | Water-based high-solid foaming resin for synthetic leather and preparation method thereof |
| CN113667089A (en) * | 2021-07-27 | 2021-11-19 | 李洪有 | Waterborne polyurethane for synthetic leather and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1185450A (en) * | 1996-12-18 | 1998-06-24 | 韦特科公司 | Synthesizing of polyurethane by functional group dead end polymer containing sulfonation group |
| US5807919A (en) * | 1996-08-13 | 1998-09-15 | H.B. Fuller Licensing & Financing, Inc. | Water-based sulfonated polymer compositions |
| CN102659994A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Use of sulfonate-type polyol as chain extender for preparing polyurethane |
| CN103242794A (en) * | 2013-04-07 | 2013-08-14 | 武汉工程大学 | Method for preparing high-solid-content sulfonic-acid waterborne polyurethane adhesive |
-
2014
- 2014-09-19 CN CN201410483653.XA patent/CN104262571B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5807919A (en) * | 1996-08-13 | 1998-09-15 | H.B. Fuller Licensing & Financing, Inc. | Water-based sulfonated polymer compositions |
| CN1185450A (en) * | 1996-12-18 | 1998-06-24 | 韦特科公司 | Synthesizing of polyurethane by functional group dead end polymer containing sulfonation group |
| CN102659994A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Use of sulfonate-type polyol as chain extender for preparing polyurethane |
| CN103242794A (en) * | 2013-04-07 | 2013-08-14 | 武汉工程大学 | Method for preparing high-solid-content sulfonic-acid waterborne polyurethane adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262571A (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262571B (en) | A kind of preparation method and applications of soft large arch dam waterborne polyurethane resin | |
| CN106496485B (en) | A kind of epoxy-modified yin/non-ionic water polyurethane resin and preparation method thereof | |
| CN106220817B (en) | A kind of no-solvent type interior leather for automobiles middle layer polyurethane resin and preparation method thereof | |
| CN104628980B (en) | A kind of method that synthetic leather is made with polyurethane resin and using the polyurethane resin in uninanned platform leather | |
| CN106397706B (en) | High rigidity epoxy modified polyurethane composite material and preparation method | |
| CN104262572B (en) | The preparation method of polyurethane prepolymer and large arch dam waterborne polyurethane resin | |
| CN103073692A (en) | Producing method of water-base polyurethane | |
| CN103709363A (en) | Sulfonate polyurethane emulsion with high solid content as well as preparation method and application thereof | |
| CN107417874B (en) | End-capped two-component solvent-free waterproof moisture-permeable polyurethane resin and preparation method thereof | |
| CN100460434C (en) | Self-emulsifying water-thinned anion polyurethane emulsion and its prepn process | |
| CN104693405A (en) | Hyperbranched polyurethane containing active amino groups and preparation method thereof | |
| CN103467687B (en) | Preparation method of solvent-free waterborne polyurethane resin | |
| CN102449045B (en) | Process for producing porous object, and porous object, layered product, and leather-like sheet each obtained thereby | |
| CN107163211A (en) | A kind of preparation method of shape memory polyurethane | |
| CN109096466A (en) | A kind of preparation method of biology base water polyurethane bass | |
| CN102731747B (en) | Dyeable dry-method artificial leather polyurethane resin, producing method and method for producing artificial leather by polyurethane resin | |
| CN109734871A (en) | A kind of low water absorbable, high solids content polyaminoester emulsion preparation method | |
| CN109734868A (en) | A kind of dedicated high high dyeing polyurethane resin of physical property of superfine fiber chemical leather and preparation method thereof | |
| CN103467693A (en) | Preparation method of waterborne polyurethane with excellent freeze-thawing stability | |
| CN109456449A (en) | Epoxy modified aqueous polyurethane of a kind of colour copoly type and preparation method thereof | |
| CN104448308A (en) | Waterborne blocked polyisocyanate cross-linking agent with polyethyleneimine skeleton and preparation method of waterborne blocked polyisocyanate cross-linking agent | |
| CN102168379A (en) | Polyurethane polymer material with high water pressure resistance and high moisture permeability | |
| CN102993400A (en) | Moisture-permeable and waterproof type no-yellowing polyurethane resin for shoe leather and preparation method | |
| CN111013506B (en) | Microcapsule emulsion of micromolecular anti-aging agent with degradable capsule wall and preparation method and application thereof | |
| CN110330618A (en) | Aqueous polyurethane emulsion, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |