CN104262571A - Preparation method and application of soft high-solid-content waterborne polyurethane resin - Google Patents
Preparation method and application of soft high-solid-content waterborne polyurethane resin Download PDFInfo
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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- C08G18/40—High-molecular-weight compounds
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- 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
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Abstract
The invention provides a preparation method of soft high-solid-content waterborne polyurethane resin. The preparation method comprises the following steps: (1) mixing and dehydrating polyester polyol of which a molecular main chain contains at least one sodium sulfonate group with mixed polyalcohol, and reacting with aromatic diisocyanate to prepare a polyurethane prepolymer; (2) adding the polyurethane prepolymer prepared in the step (1) into small-molecular dihydric alcohol, and terminating; (3) diluting and emulsifying acetone, and adding an amine chain extender to react to prepare a polyurethane dispersion liquid; and (4) removing acetone in the polyurethane dispersion liquid to obtain the waterborne polyurethane resin. The preparation method provided by the invention is wide in applicability, and can be used for preparing soft waterborne polyurethane resin with different performance requirements and applications; and the prepared waterborne polyurethane resin provided by the invention has the advantages of high solid content, soft and elastic film forming, good low-temperature flexibility, high cost performance and the like, and can be widely applied to soft coating or decoration in the fields of textiles, leathers, synthetic leathers and the like.
Description
Technical field
The invention belongs to waterborne polyurethane resin preparation field, especially relate to and there is large arch dam and preparation method that is soft or waterborne polyurethane resin that kindliness is good.
Background technology
Urethane resin, as a kind of high performance polymer material, has a wide range of applications in various field.Traditional polyurethane material mainly solvent borne polyurethane, containing a large amount of organic solvents, causes serious harm to environment and human body.Aqueous polyurethane take water as dissolve medium, does not contain or on a small quantity containing organic solvent, significantly decreases the discharge of volatilizable organism (VOC), and save the energy and resource.Along with countries in the world government and the pay attention to day by day to environmental protection among the people, also all the more strict to the restriction of VOC discharge, use urethane replaces solvent borne polyurethane to be a development trend, and the field such as tackiness agent, coating, coating, ink of aqueous polyurethane, prospect is very wide.
Due to technical elements, aqueous polyurethane solid content commercially available is at present on the low side (being generally no more than 40%), and cause rate of drying slow, film forming is not plentiful, and increases transportation cost, energy expenditure when increasing dry.
The research and development of high-solid content water-based polyurethane is an important trend, in patent CN102206410B, preparation method's step comprise prepolymerization reaction (preparing prepolymer), monomer modified, in and the step such as salify and emulsification chain extension, adopt the method that carboxylic acid type and sulfonic acid type hydrophilic chain extender combine, using aliphatics and alicyclic diisocyanate as isocyanate-monomer, prepared the waterborne polyurethane resin of solid content at 50-60%, this resin can be used for synthetic leather field; Because aliphatic isocyanates price is higher, add the materials such as organosilicon, high expensive simultaneously, be unfavorable for large-scale industrialization promotion.
In patent CN103360563, preparation method's step comprises polyurethane preformed polymer, mixing urethane obtained emulsion after aggressiveness, chain extension.Adopt quadrol base ethyl sulfonic acid sodium as hydrophilic chain extender, isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) are as isocyanate-monomer, prepare the waterborne polyurethane resin that solid content reaches 50%, the polyurethane prepolymer of preparation also will through the interlinkage polymerization of two, there is high expensive in this technique, is unfavorable for large-scale promotion equally.
In patent CN103613730A, also the step such as preparation and chain extension of prepolymer is comprised in preparation method, also adopt quadrol base ethyl sulfonic acid sodium as hydrophilic chain extender, isophorone diisocyanate, as isocyanate-monomer, obtains stable nano-silicon dioxide modified large arch dam waterborne polyurethane resin.Because quadrol base ethyl sulfonic acid sodium is containing two highly active amido hydrophilic chain extenders, quick with the reaction of isocyanic ester, generally need to add reaction at a lower temperature, and need to add in the later stage of reaction, therefore generally can only adopt active relatively low isocyanate-monomer (as IPDI, HDI), and these two kinds of monomers often price is higher, significantly improve the cost of large arch dam waterborne polyurethane resin.
Summary of the invention
The present invention proposes a kind of preparation method of large arch dam waterborne polyurethane resin, preparation cost is relatively low, the waterborne polyurethane resin of various different performance requirement and purposes can be prepared, adopt polyester polyol molecular backbone chain containing at least one sodium group as hydrophilic chain extender, join in reaction system at the polyreaction initial stage, be reacted to more equably in polyurethane molecular chain.
The technical solution used in the present invention is as follows:
The preparation method of the large arch dam waterborne polyurethane resin of a kind of softness that one aspect of the present invention provides, step is as follows:
1) by after the polyester polyol containing at least one sodium group on molecular backbone chain, polyol blend mixed dehydration, react with aromatic diisocyanate, obtained polyurethane prepolymer;
2) by step 1) polyurethane prepolymer prepared adds small molecules dibasic alcohol, end-blocking;
3) after acetone diluted, emulsification, amine chainextender reaction is added, obtained polyurethane dispersing liquid;
4) remove the acetone in above-mentioned polyurethane dispersing liquid, obtain waterborne polyurethane resin.
Above-mentioned preparation method, further preferably, concrete steps are as follows:
1) under nitrogen protection, stir on molecular backbone chain containing the polyester polyol of at least one sodium group and polyol blend heat fused, at 110-130 DEG C, decompression dehydration 1-2 hour under vacuum tightness 0.09-0.1MPa; Be cooled to 50-60 DEG C, add acetone adjusting viscosity, after stirring, add aromatic diisocyanate, be warming up to 70-90 DEG C and after reacting 1-3 hour, obtained polyurethane prepolymer;
2) step 1) in preparation polyurethane prepolymer add small molecules dibasic alcohol end-blocking, react to NCO theoretical value;
3) acetone diluted step 2) prepared by reactant, under high shear, add deionized water and carry out emulsification 1-2min, after emulsification terminates, under stirring, add amine chainextender, and continue stir 5-10min, obtain polyurethane dispersing liquid;
4) step 3) polyurethane dispersing liquid prepared is heated to 45-55 DEG C, and the acetone in the above-mentioned polyurethane dispersing liquid of removed under reduced pressure, obtains waterborne polyurethane resin.
In above-mentioned preparation method, further preferably, on described molecular backbone chain containing the polyester polyol of at least one sodium group be through the molecular weight of oversulfonate be the poly-fumaric acid-hexanodioic acid-ethylene glycol of 800-3000, poly-fumaric acid-hexanodioic acid-glycol ether ester polyol or poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol;
Described polyol blend is the molecular weight polyester polyol that is 500-3000 or polyether glycol or mixture both it;
Described small molecules dibasic alcohol is selected from one or more mixtures of ethylene glycol, 1,3-PD, 1,2-PD, BDO, 1,3 butylene glycol, glycol ether, 1,6-hexylene glycol;
Described aromatic diisocyanate is tolylene diisocyanate;
Described amine chainextender is selected from one or more mixtures in quadrol, hexanediamine, piperazine, 2,5-lupetazins, isophorone diamine, 4-4 '-diamino cyclohexyl-methane, Isosorbide-5-Nitrae-diamino-cyclohexane, hydrazine, adipic dihydrazide.
Further preferably, described molecular backbone chain is be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000 through the molecular weight of oversulfonate containing the polyester polyol of at least one sodium group;
Described polyol blend is polyethylene glycol adipate glycol, polyneopentyl glycol adipate glycol, the poly-hexanodioic acid-1 of 1000-2000,4-butanediol ester glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-epsilon-caprolactone glycol, polycarbonate diol or PTMG;
Described small molecules dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol;
Described amine chainextender is selected from quadrol, hexanediamine, piperazine, 2,5-lupetazins, isophorone diamine.
Further preferably, described molecular backbone chain is be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000 through the molecular weight of sodium bisulfite sulfonation containing the polyester polyol of at least one sodium group;
Polyethylene glycol adipate glycol, polyneopentyl glycol adipate glycol, the poly-hexanodioic acid-BDO esterdiol of described polyol blend to be molecular weight be 1000-2000;
Described small molecules dibasic alcohol is BDO;
Described amine chainextender is selected from quadrol, piperazine, 2,5-lupetazins, isophorone diamine.
Further preferably, on described molecular backbone chain containing the polyester polyol of at least one sodium group be through the molecular weight of sodium bisulfite sulfonation be 1000-2000, acid number is lower than the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol of 0.3mgKOH/g; Described amine chainextender is isophorone diamine.
Wherein, the above-mentioned molecular weight through oversulfonate is the poly-fumaric acid-hexanodioic acid-ethylene glycol of 800-3000, poly-fumaric acid-hexanodioic acid-glycol ether ester polyol or poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol or be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000 preferable through the molecular weight of sulfonation, containing at least one sodium group on main chain, be through oversulfonate, containing at least one sodium group on molecular backbone chain, molecular weight is the poly-fumaric acid-hexanodioic acid-ethylene glycol of 800-3000, poly-fumaric acid-hexanodioic acid-glycol ether ester polyol or poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol or preferable through sulfonation, containing at least one sodium group on molecular backbone chain, molecular weight is the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000.
Above-mentioned polyol blend, small molecules dibasic alcohol and amine chainextender can adopt the arbitrary proportion mixture of described compound, because described compound in the polymerization, the function of enforcement is close.
In addition, in above-mentioned reaction, the weight percent of each reaction raw materials is as follows:
Polyester polyol 5 ~ 20%, described polyol blend 70 ~ 80%, described aromatic diisocyanate 10 ~ 22%, described small molecules dibasic alcohol 2 ~ 4%, described amine chainextender 1 ~ 2% containing at least one sodium group on described molecular backbone chain;
Step 3) described in acetone consumption be step 2) in prepared reactant weight 80 ~ 100%; The water content of described acetone is lower than 3000ppm.Wherein, acetone as solvent, the performances such as adjusting viscosity.
Further preferably, the weight percent of the polyester polyol containing at least one sodium group on described molecular backbone chain is 10 ~ 15%.
In above-mentioned preparation method, NCO theoretical value is less than or equal to 1.1% ~ 1.2%.
On the other hand, in the application, the coating being applied to weaving, leather or synthetic leather of the large arch dam waterborne polyurethane resin of softness prepared by aforesaid method; Further, the large arch dam waterborne polyurethane resin that prepared by aforesaid method is applied to leather limit oil or synthetic leather wet method foamed slurry.
Sulfonation reaction, a kind of any chemical process introducing sulfonic group (-SO3H) or its corresponding salt or sulphonyl halogen in organic compound molecule, containing at least containing a sulfonic group in the molecular backbone chain of the organic compound after sulfonation reaction.
Polyester polyol containing at least one sodium group on molecular backbone chain, add the surfactivity of polyvalent alcohol, sulfonic group on its Middle molecule can be replaced by other groups further, activity is higher, in prepolymer reaction, polyester polyol containing sodium group on molecular backbone chain, when other polyester polyols (being different from the former) and aromatic diisocyanate polyreaction, the hydroxyl of NCO group and polyester polyol carries out reaction and forms main polymer chain, sulfonic acid group can by hydroxyl, amino groups replaces, be conducive to prepolymer macromole or cancellated formation.Aromatic diisocyanate is as tolylene diisocyanate, when preparing water dispersion, easily creating many precipitations, causing stability to decline, utilize the polyester polyol containing sodium group on highly active molecular backbone chain, the polyurethane prepolymer of formation has good dispersiveness and stability in storage; Especially adopt tolylene diisocyanate, have phenyl ring, the molecule forming polymkeric substance has more outstanding stability; And the price of aromatic diisocyanate is lower, and preparation cost is lower.
In addition, poly-fumaric acid-hexanodioic acid-ethylene glycol is polymerized by fumaric acid, hexanodioic acid and ethylene glycol to be prepared from; Poly-fumaric acid-hexanodioic acid-glycol ether ester polyol is prepared from by fumaric acid, hexanodioic acid, glycol ether; Poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol or poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol are prepared from by fumaric acid, hexanodioic acid, ethylene glycol and glycol ether; Wherein fumaric acid, is also called butene dioic acid, and hexanodioic acid is all two carboxylic acid, and ethylene glycol and glycol ether are all dibasic alcohol, can with reference to preparation methods such as polyethylene glycol adipate dibasic alcohol.
Amine chainextender adopts quadrol, hexanediamine, piperazine etc. containing two amino compound, further preferably, adopt the organic heterocyclic molecule such as isophorone diamine, piperazine or derivatives thereof, there is higher formulating of recipe degree of freedom, in polymkeric substance, the existence of heterocycle structure makes waterborne polyurethane resin have good intensity and hardness exists, strengthen quick-dry type, there is chromaticity stability and form, stability in storage simultaneously.
In preparation process, the polyester polyol containing sodium group and other polyol blends can join in reaction in early stage in advance, directly add vulcabond subsequently and carry out polyreaction, and form polyurethane prepolymer, preparation method is relatively simple; End-blocking subsequently and add in amine chainextender curing reaction, do not need a large amount of acetone to participate in reaction, the use of acetone in relatively current preparation method, in the application, acetone consumption is less, shortens the recover acetone time.
The application preparation method suitability is wide, can prepare the soft waterborne polyurethane resin of various different performance requirement and purposes; The solid content of prepared waterborne polyurethane resin is high, film forming soft flexible, low-temperature flexibility good, cost performance advantages of higher, can be widely used in soft coating or the decoration in the fields such as placement, leather, synthetic leather.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The preparation method of the large arch dam waterborne polyurethane resin that embodiment 1 one kinds is soft
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
By on 200g main chain containing at least one sodium group, molecular weight be 2000 poly-fumaric acid-hexanodioic acid-glycol ether ester polyol and 1400g molecular weight be 2000 poly-hexanodioic acid-1,4-butanediol ester glycol is put in reactor, and intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 260g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 40g ethylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 1900g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1930g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 26g isophorone diamine, 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.
The preparation method of the large arch dam waterborne polyurethane resin that embodiment 2 one kinds is soft
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
By 220g molecular weight be 2000 poly-fumaric acid-hexanodioic acid-glycol ether ester polyol and 1400g molecular weight be 2000 poly-hexanodioic acid-neopentyl glycol esterdiol put in reactor, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 278g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 60g 1,6-hexylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.2%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 29.5g isophorone diamine, 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.
The preparation method of embodiment 3 one kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
300g main chain is contained at least one sodium group, molecular weight be 3000 poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol and 1500g molecular weight be 2000 PTMG put in reactor, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 280.5g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 30g ethylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 10g quadrol, 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.
The preparation method of embodiment 4 one kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
100g main chain is contained at least one sodium group, molecular weight be 800 poly-fumaric acid-hexanodioic acid-ethylene glycol and 1600g molecular weight be 500 polyethylene glycol adipate glycol put in reactor, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds 200g acetone, add 200g tolylene diisocyanate (TDI) after stirring, be warming up to 70 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 60g 1,3-PD and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 40g 4-4 '-diamino cyclohexyl-methane, and continue to stir 5-10min, obtain 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.
The preparation method of embodiment 5 one kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
100g main chain is contained at least one sodium group, molecular weight be 1000 poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol and 1400g molecular weight be 1500 poly-hexanodioic acid-1,4-butanediol ester glycol is put in reactor, and intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 440g tolylene diisocyanate (TDI) after stirring, be warming up to 90 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 40g ethylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 20g quadrol, and continue to stir 5-10min, obtain polyurethane dispersing liquid.Dispersion liquid is heated to 55 DEG C, the acetone under-0.1MPa in removed under reduced pressure dispersion liquid, obtains waterborne polyurethane resin.
The preparation method of embodiment 6 one kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
200g main chain is contained at least one sodium group, molecular weight be 2000 poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol and 1500g molecular weight be 2000 poly-epsilon-caprolactone glycol put in reactor, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds 200g acetone, add 200g tolylene diisocyanate (TDI) after stirring, be warming up to 70 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 70g glycol ether and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 30g piperazine, and continue to stir 5-10min, obtain 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.
The preparation method of embodiment 7 one kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
200g main chain is contained at least one sodium group, molecular weight be 2000 poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol and 1500g molecular weight be 2000 polycarbonate diol put in reactor, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 50 DEG C, adds 200g acetone, add 200g tolylene diisocyanate (TDI) after stirring, be warming up to 70 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 70g glycol ether and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 2000g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1980g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 30g 2,5-lupetazin, and continue to stir 5-10min, obtain 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.
The preparation method of embodiment 8 one kinds of large arch dam waterborne polyurethane resins
Be with the difference of embodiment 7: the mixture adopting piperazine and 2,5-lupetazin, mixed weight ratio is 1:2; Adopt poly-epsilon-caprolactone glycol and polycarbonate diol mixture, mixed weight ratio is 1:3; Adopt the mixture of 1,3-PD, 1,2-PD, mixed weight ratio is 1:3.
The preparation method of the large arch dam waterborne polyurethane resin that embodiment 9 one kinds is soft
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
By on 210g molecular backbone chain containing the polyester polyol of at least one sodium group be through the molecular weight of sodium bisulfite sulfonation be 2000, acid number lower than the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol of 0.3mgKOH/g and 1400g molecular weight be 2000 poly-hexanodioic acid-1,4-butanediol ester glycol is put in reactor, and intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 260g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 40g BDO and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 1900g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1930g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 26g isophorone diamine, 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.
The preparation method of embodiment 10 1 kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
By on 210g molecular backbone chain containing the polyester polyol of at least one sodium group be through the molecular weight of sodium bisulfite sulfonation be 2000, acid number is that the PTMG of 1500 and the mixture (mixed weight ratio 1:2) of polycarbonate diol are put in reactor lower than the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol of 0.3mgKOH/g and 1400g molecular weight, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 60 DEG C, adds 200g acetone, add 260g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 40g 1,6-hexylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 1900g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1930g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 26g isophorone diamine, 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.
The preparation method of embodiment 11 1 kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
By on 200g molecular backbone chain containing at least one sodium group, through the molecular weight of sodium bisulfite sulfonation be 2000, acid number is that the PTMG of 1500 and the mixture of polycarbonate diol are put in reactor lower than the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol of 0.3mgKOH/g and 1400g molecular weight, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 55 DEG C, adds 200g acetone, add 300g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 60g 1,6-hexylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 1900g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1930g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 40g hydrazine, 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.
The preparation method of embodiment 12 1 kinds of large arch dam waterborne polyurethane resins
The preparation method of large arch dam waterborne polyurethane resin, step is as follows:
To 300g molecular backbone chain be 1600 gather fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol and 1400g molecular weight is that the PTMG of 1500 and the mixture (mixed weight ratio is 1:5) of polycarbonate diol are put in reactor through sodium bisulfite sulfonation containing at least one sodium group, molecular weight, intensification heat fused also stirs.At 120 DEG C, decompression dehydration 1 hour under vacuum tightness 0.1MPa.Dehydration terminates, and is cooled to 55 DEG C, adds 200g acetone, add 200g tolylene diisocyanate (TDI) after stirring, be warming up to 80 DEG C and react 2 hours, obtaining polyurethane prepolymer.
Subsequently, add 60g 1,6-hexylene glycol and continue reaction 2 hours, if record NCO% to be less than or equal to 1.1%, then react end.Be added drop-wise in reactant with 1900g acetone and carry out diluting and lowering the temperature.Acetone dropwises, and under high shear, adds 1930g deionized water and carries out emulsification 1-2min.
After emulsification terminates, add 40g adipic dihydrazide, 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.
The preparation method of embodiment 13 1 kinds of large arch dam waterborne polyurethane resins
Distinguish with embodiment 12 and be: adopt poly-hexanodioic acid-1,4-butanediol ester glycol, poly-hexanodioic acid-1, the mixture (mixed weight ratio is 1:2) of 6-hexylene glycol esterdiol is as polyol blend, adopt the mixture (mixed weight ratio is 1:4) of adipic dihydrazide and Isosorbide-5-Nitrae-diamino-cyclohexane as amine chainextender; Adopt BDO end-blocking.
The solid content of the waterborne polyurethane resin prepared in above-described embodiment is high can reach 50%, soft and soft, and elasticity is better.The salient features preparing waterborne polyurethane resin in embodiment 1-3 is as shown in table 1:
Table 1:
The salient features of the waterborne polyurethane resin prepared in embodiment 9-11 is as shown in table 2:
Table 2:
Wherein, waterborne polyurethane resin outward appearance prepared by embodiment 1-7 embodiment 8 ~ 13 presents milky white band blue light, and solid content is on average more than 50%, and storage cycle is longer; Resin also can show outstanding performance in the mechanical property of film, illustrates that the hard section of waterborne polyurethane resin of preparation and soft section reach balance, both can keep excellent softness, and have outstanding mechanical strength performance simultaneously.
Waterborne polyurethane resin prepared by above-described embodiment be applied to weaving, leather or synthetic leather coating or be applied to leather limit oil or synthetic leather wet method foamed slurry, utilize the preparation method of this area routine, raw material comprises the material such as waterborne polyurethane resin, colorant, defoamer, sanitas, flow agent prepared by above-described embodiment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for soft large arch dam waterborne polyurethane resin, it is characterized in that, step is as follows:
1) by after the polyester polyol containing at least one sodium group on molecular backbone chain, polyol blend mixed dehydration, react with aromatic diisocyanate, obtained polyurethane prepolymer;
2) by step 1) polyurethane prepolymer prepared adds small molecules dibasic alcohol, end-blocking;
3) after acetone diluted, emulsification, amine chainextender reaction is added, obtained polyurethane dispersing liquid;
4) remove the acetone in above-mentioned polyurethane dispersing liquid, obtain waterborne polyurethane resin.
2. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as claimed in claim 1, it is characterized in that, concrete steps are as follows:
1) under nitrogen protection, stir on molecular backbone chain containing the polyester polyol of at least one sodium group and polyol blend heat fused, at 110-130 DEG C, decompression dehydration 1-2 hour under vacuum tightness 0.09-0.1MPa; Be cooled to 50-60 DEG C, add acetone adjusting viscosity, after stirring, add aromatic diisocyanate, be warming up to 70-90 DEG C and after reacting 1-3 hour, obtained polyurethane prepolymer;
2) step 1) in preparation polyurethane prepolymer add small molecules dibasic alcohol end-blocking, react to NCO theoretical value;
3) acetone diluted step 2) prepared by reactant, under high shear, add deionized water and carry out emulsification 1-2min, after emulsification terminates, under stirring, add amine chainextender, and continue stir 5-10min, obtain polyurethane dispersing liquid;
4) step 3) polyurethane dispersing liquid prepared is heated to 45-55 DEG C, and the acetone in the above-mentioned polyurethane dispersing liquid of removed under reduced pressure, obtains waterborne polyurethane resin.
3. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as described in any one of claim 1 or 2, is characterized in that: on described molecular backbone chain containing the polyester polyol of at least one sodium group be through the molecular weight of oversulfonate be the poly-fumaric acid-hexanodioic acid-ethylene glycol of 800-3000, poly-fumaric acid-hexanodioic acid-glycol ether ester polyol or poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether polyvalent alcohol;
Described polyol blend is the molecular weight polyester polyol that is 500-3000 or polyether glycol or mixture both it;
Described small molecules dibasic alcohol is selected from one or more mixtures of ethylene glycol, 1,3-PD, 1,2-PD, BDO, 1,3 butylene glycol, glycol ether, 1,6-hexylene glycol;
Described aromatic diisocyanate is tolylene diisocyanate;
Described amine chainextender is selected from one or more mixtures in quadrol, hexanediamine, piperazine, 2,5-lupetazins, isophorone diamine, 4-4 '-diamino cyclohexyl-methane, Isosorbide-5-Nitrae-diamino-cyclohexane, hydrazine, adipic dihydrazide.
4. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as claimed in claim 3, is characterized in that: described molecular backbone chain is be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000 through the molecular weight of oversulfonate containing the polyester polyol of at least one sodium group;
Described polyol blend is polyethylene glycol adipate glycol, polyneopentyl glycol adipate glycol, the poly-hexanodioic acid-1 of 1000-2000,4-butanediol ester glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-epsilon-caprolactone glycol, polycarbonate diol or PTMG;
Described small molecules dibasic alcohol is selected from ethylene glycol, BDO, 1,6-hexylene glycol;
Described amine chainextender is selected from quadrol, hexanediamine, piperazine, 2,5-lupetazins, isophorone diamine.
5. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as claimed in claim 4, is characterized in that: described molecular backbone chain is be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester polyol of 1000-2000 through the molecular weight of sodium bisulfite sulfonation containing the polyester polyol of at least one sodium group;
Polyethylene glycol adipate glycol, polyneopentyl glycol adipate glycol, the poly-hexanodioic acid-BDO esterdiol of described polyol blend to be molecular weight be 1000-2000;
Described small molecules dibasic alcohol is BDO;
Described amine chainextender is selected from quadrol, piperazine, 2,5-lupetazins, isophorone diamine.
6. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as claimed in claim 5, is characterized in that: described molecular backbone chain is be the poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol of 1000-2000 through the molecular weight of sodium bisulfite sulfonation containing the polyester polyol of at least one sodium group; Described amine chainextender is isophorone diamine; Described poly-fumaric acid-hexanodioic acid-ethylene glycol-glycol ether ester dibasic alcohol acid number is lower than 0.3mgKOH/g.
7. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as described in any one of claim 1 or 2, it is characterized in that, the weight percent of each reaction raw materials is as follows:
Polyester polyol 5 ~ 20%, described polyol blend 70 ~ 80%, described aromatic diisocyanate 10 ~ 22%, described small molecules dibasic alcohol 2 ~ 4%, described amine chainextender 1 ~ 2% containing at least one sodium group on described molecular backbone chain;
Step 3) described in acetone consumption be step 2) in prepared reactant weight 80 ~ 100%; The water content of described acetone is lower than 3000ppm.
8. the preparation method of the large arch dam waterborne polyurethane resin of a kind of softness as claimed in claim 7, is characterized in that: the weight percent of the polyester polyol containing at least one sodium group on described molecular backbone chain is 10 ~ 15%.
9. the coating being applied to weaving, leather and synthetic leather of the large arch dam waterborne polyurethane resin of the softness prepared by any one of claim 1-8.
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| 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 |
| CN114057987A (en) * | 2020-08-03 | 2022-02-18 | 东成化学有限公司 | Water-dispersible polyurethane-urea resin composition for synthetic leather and preparation 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 |
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| CN104262571B (en) | 2018-05-15 |
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