CN103467687A - Preparation method of solvent-free waterborne polyurethane resin - Google Patents
Preparation method of solvent-free waterborne polyurethane resin Download PDFInfo
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- CN103467687A CN103467687A CN2013104425877A CN201310442587A CN103467687A CN 103467687 A CN103467687 A CN 103467687A CN 2013104425877 A CN2013104425877 A CN 2013104425877A CN 201310442587 A CN201310442587 A CN 201310442587A CN 103467687 A CN103467687 A CN 103467687A
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Abstract
The invention discloses a preparation method of a solvent-free waterborne polyurethane resin. The preparation method specifically comprises: (1), adding amino type cage type silsesquioxane into excessive isocyanate monomers at 20-80 DEG C, reacting until the solution is clear; (2), adding ethyoxyl sealed polymer glycol, hydrophilic functional monomer, dihydric alcohol and catalyst di-n-butyltin dilaurate into the solution obtained in the step (1) (wherein the R value is controlled to be 1.50-3.00 during a pre-polymerization reaction process), reacting for 1-2h at 40-70 DEG C, then heating to 70-90 DEG C, keeping reacting for 1-2h, and then cooling to normal temperature; (3), adding neutralizer and water into the solution obtained in the step (2), and diffusing; and (4), adding a chain extender at 30-50 DEG C, carrying out chain extending reaction for 2-4h, and cooling to normal temperature, so as to obtain the waterborne polyurethane. The solvent-free waterborne polyurethane resin prepared by the method disclosed by the invention has excellent viscosity, adhesive strength and wearing resistance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of preparation method of solvent-free waterborne polyurethane resin.
Background technology
Aqueous polyurethane is to using water to substitute as dispersion agent the emerging macromolecular material that organic solvent grows up, the molecular structure that it is special and state of aggregation, make it there is the performances such as excellent erosion resistant, snappiness, sticking power and chemical-resistant, its formed good mechanical property of filming, wear resistance is good, hardness is high, water-fast, chemically-resistant, the excellent properties such as ageing-resistant, can be widely used in the fields such as light textile, printing and dyeing, leather processing, coating, tackiness agent, wood working, building and papermaking.
The preparation method of aqueous polyurethane can be divided into two kinds of outer emulsion process and self-emulsifications.Outer emulsion process claims again forced emulsification, and the method refers to the base polyurethane prepolymer for use as of certain molecular weight or prepolymer solution are added to emulsifying agent, under strong stirring, it is scattered in water, makes corresponding polyaminoester emulsion or dispersion.This is the method for preparing in early days aqueous polyurethane.Polyaminoester emulsion particle diameter prepared by outer emulsion process is larger, generally is greater than 0.1 μ m, the outward appearance gonorrhoea, and stability in storage is poor, owing to using more emulsifying agent, makes the film-forming properties of product bad, and affects water tolerance, intensity, toughness and the cementability of glued membrane.Self-emulsification is called again the internal emulsification method, refers in the urethane segment and contains hydrophilic composition, thereby can form the method for stable emulsion without emulsifying agent.Comparatively speaking, in the emulsion prepared with outer emulsion process, the performance of polyurethane laminate after remaining hydrophilic small molecules emulsifying agent can affect and solidify, and self-emulsifying can be eliminated this disadvantage.Self-emulsification is divided into: acetone method, prepolymer method, melting dispersion method and ketoimine-one azine method.
Wang Qi (CN201010622595.6) and learn equal (CN02159275.6) and take N methyldiethanol amine and make self-emulsifying cation type aqueous polyurethane as the wetting ability function monomer.Fu and green grass or young crops (CN100480349C) obtain modifier modification epoxy resin the epoxy resin of modification, by polyisocyanates and polyester or polyether glycol reaction, then add chainextender, obtain base polyurethane prepolymer for use as, use the modified epoxy modified polyurethane prepolymer, obtain the base polyurethane prepolymer for use as of modification, finally the base polyurethane prepolymer for use as of modification is added to water and disperse with high speed dispersor, add neutralizing agent and linking agent, obtain modified aqueous adhesion agent of polyurethane.
The waterborne polyurethane resin of present stage is prepared with two processes, at first be the synthetic of wetting ability performed polymer, secondly be that performed polymer is neutralized, be scattered in water, then chain extension obtains final aqueous polyurethane, in these two processes, the viscosity of system is a very important factor that affects product quality.In synthetic performed polymer process, system viscosity is high, can cause that mixing of materials is inhomogeneous and the difficulty of conducting heat, and is unfavorable for obtaining stable dispersion.Viscosity problem for performed polymer, the tradition solution is to add a large amount of lower boiling organic solvents to help viscosity reduction, obtain removing organic solvent by the method vacuumized again after product, the shortcoming of this kind of method is to have consumed a large amount of organic solvents and the energy, residual in system have a part volatile organic solvent, environment is had to certain pollution, and the product simultaneously prepared all has the shortcoming that intensity is not high, wear resistance is general, therefore is difficult to meet the needs in growing market.
Summary of the invention
The object of the invention is to provide in order to overcome above the deficiencies in the prior art a kind of preparation method of solvent-free waterborne polyurethane resin.
In order to achieve the above object, the present invention adopts following technique means to carry out:
A kind of preparation method of solvent-free waterborne polyurethane resin, carry out in the steps below:
(1) under 20-80 ℃, the amino-type cage-type silsesquioxane is joined in isocyanate-monomer, reaction is to limpid;
(2) add oxyethyl group terminated polymer glycol, wetting ability function monomer, dibasic alcohol and catalyzer di-n-butyltin dilaurate in (1) products therefrom, controlling the R value in the prepolymerization reaction process is 1.50-3.00, is warming up to 70-90 ℃ and continues to be down to room temperature after reaction 1-2h after 40-70 ℃ of reaction 1-2h; The ratio of the mole number of total OH group in the mole number that above-mentioned R value refers in system total NCO group and system;
(3) in (2) products therefrom, add neutralizing agent and water to be disperseed;
(4) add chainextender to carry out chain extending reaction 2-4h in 30-50 ℃, be down to room temperature, obtain aqueous polyurethane.
The preparation method of described solvent-free waterborne polyurethane resin, the described amino-type cage-type silsesquioxane of step (1) can be any one in following T8, T10, T12 or T14 structure:
R is-CH
2-CH
2-CH
2-NH
2.
The described isocyanate-monomer of step (1) can be tolylene diisocyanate, ditan-4,4-vulcabond, 1, hexamethylene-diisocyanate, isophorone diisocyanate, methylene radical-dicyclohexyl-4, a kind of in 4-vulcabond or Methylcyclohexyl diisocyanate.
The described oxyethyl group terminated polymer of step (2) glycol can be for having a kind of in following structure (I) or structure (II):
（Ⅱ）
Wherein n is 1-1000.
The described wetting ability function monomer of step (2) can be dimethylol propionic acid, N methyldiethanol amine, N, N-dimethylethanolamine, N, N-dimethyl-ethylenediamine or N, a kind of in the N-diethyl ethylenediamine.
The described dibasic alcohol of step (2) can be polyether Glycols, polyester diol, polyester polyethers mixing dibasic alcohol, polyoxypropyleneglycol, polybutadiene diol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-tetrahydrochysene fluorine mutter glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-epsilon-caprolactone glycol or polycarbonate-1, a kind of in 6-hexylene glycol esterdiol.
The described neutralizing agent of step (3) can be in ammoniacal liquor or acetic acid a kind of.
The described chainextender of step (4) is can quadrol, 1,2-propylene diamine, 1,3-propylene diamine, Putriscine, 1, a kind of in 6-hexanediamine or Isosorbide-5-Nitrae-pentamethylene diamine.
The preparation method of described solvent-free waterborne polyurethane resin, wherein adding the mass ratio of amino-type cage-type silsesquioxane and isocyanate-monomer in step (1) is 1.384-2.775:1; The mass ratio that adds oxyethyl group terminated polymer glycol, wetting ability function monomer, dibasic alcohol and catalyzer di-n-butyltin dilaurate in step (2) is 22-32.7:114.94-183.48:8.81-12.88:1; It is 0.439-0.454:1 that step (3) adds the mass ratio of neutralizing agent and wetting ability function monomer; Adding the mass ratio of chainextender and oxyethyl group terminated polymer glycol in step (4) is 0.777-0.886:1.
The invention provides a kind of waterborne polyurethane resin of high combination property, and there is following features:
(1) the present invention at first will contain the amino-type cage-type silsesquioxane carry out isocyanate-terminated after, carry out the building-up reactions of performed polymer together with oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent alcohol, but effectively avoided amino-type cage-type silsesquioxane salify wetting ability function monomer together with dibasic alcohol when charging and isocyanate reaction, because of the amino active high gelation that occurs.
(2) with traditional aqueous polyurethane, compare, the present invention introduces the cage-type silsesquioxane molecular structure in the molecular structure main chain of waterborne polyurethane resin, inorganic molecular structure is embedded in organic molecular structure, obtain the urethane resin of inorganic hybridization, when not affecting the good characteristic of resin own, especially can improve consistency and the cohesive force of resin and inorganic substrate.
(3) cage-type silsesquioxane has the molecular structure of high functionality, for polyurethane laminate provides high strength.
(4) cage-type silsesquioxane has high hardness, and synthetic urethane resin embodies wear resistance preferably as raw material to adopt it.
(5) there is the cage silsesquioxane structure of 3-D solid structure, play the conduct that nanometer strengthens, improve the comprehensive physical performance of urethane.
(6) but introduce hydrophilic ether chain and salify hydrophilic segment in the present invention in the urethane resin molecular side chain, the urethane resin made is Water-borne modification have stability in storage preferably very easily.
(7) have the oxyethyl group terminated polymer glycol of long ether chain side group, the viscosity that can effectively regulate urethane resin, make solvent-free urethane resin have relatively low viscosity.
(8) waterborne polyurethane resin that the present invention makes is no-solvent type, has the characteristics of zero VOC discharge.
Solvent-free aqueous polyurethane provided by the invention is compared and is had obvious performance advantage with existing conventional aqueous polyurethane, and its medium viscosity has reached below 50cp, and more than cohesive strength has reached 6.1MPa, wear resistance has reached below 0.51%.
Embodiment
Embodiment 1
Under 70 ℃, 88.00g amino-type cage-type silsesquioxane T8 is joined in the tolylene diisocyanate of 191.00g, after reaction is extremely limpid, add wherein 2 of 48.00g, 2-dihydroxymethyl butoxy ethylene glycol (20EO) methyl ether (oxyethyl group terminated polymer glycol, shown in (I), n=20 wherein), the poly-dihydric alcohol 1000 of 200.00g, the dimethylol propionic acid of 19.20g and the catalyzer di-n-butyltin dilaurate of 1.76g, in 60 ℃ of reaction 2h; Then being warming up to 85 ℃ continues to be down to room temperature after reaction 2h, then the deionized water that adds wherein 8.43g neutralizing agent ammoniacal liquor and 890.00g is disperseed 5min, add the quadrol of 40.68g to carry out chain extending reaction 3h in 40 ℃ again, be down to room temperature, obtain aqueous polyurethane.
Condition and the parameter of embodiment 2-9 reaction process see the following form 1.
Table 1 embodiment 2-9 respectively walks reaction conditions and parameter
Continued 1
For the performance situation of aqueous polyurethane provided by the invention can be described better, the present invention commonly uses the preparation of waterborne polyurethane according to conventional means, and as a comparison case, preparation process is as follows:
Comparative Examples 1
Under 70 ℃, acetone by 8.03g propylene glycol, 360.00g cetomacrogol 1000,4.00g glycerol, 61.40g trishydroxymethyl propionic acid, 395.52g isophorone diisocyanate, 1.57g di-n-butyltin dilaurate and 740.00g, be heated to 60 ℃ of reactions and be warming up to 80 ℃ after 2h and continue to be down to room temperature after reaction 2h, obtain base polyurethane prepolymer for use as; Under 25 ℃, add 32.96g ammoniacal liquor in performed polymer, then add the 720.00g deionized water to be disperseed 5min.After 40 ℃ of quadrols that add 26.94g carry out chain extending reaction 3h, be down to room temperature again, obtain aqueous polyurethane.
Comparative Examples 2
Under 70 ℃, acetone by 8.03g propylene glycol, 360.00g cetomacrogol 1000,4.00g glycerol, 60.16g trishydroxymethyl propionic acid, 380.00g tolylene diisocyanate, 1.46g di-n-butyltin dilaurate and 650.00g, be heated to 60 ℃ of reactions and be warming up to 80 ℃ after 2h and continue to be down to room temperature after reaction 2h, obtain base polyurethane prepolymer for use as; Under 25 ℃, add 32.29g ammoniacal liquor in performed polymer, then add the 670.00g deionized water to be disperseed 5min.After 40 ℃ of quadrols that add 39.29g carry out chain extending reaction 3h, be down to room temperature again, obtain aqueous polyurethane.
The preparation-obtained aqueous polyurethane of the aqueous polyurethane that Comparative Examples is prepared and embodiment carries out the performance test simultaneous test, and concrete outcome is in Table 2.
The waterborne polyurethane resin performance test made in table 2 embodiment 1-9 and Comparative Examples 1-2
Can find out from above testing data, obviously be better than existing conventional aqueous polyurethane on solvent-free Property of Waterborne Polyurethane provided by the invention, at solvent-free aqueous polyurethane provided by the invention aspect viscosity, cohesive strength and wear resistance, there is very large advantage.
Claims (9)
1. the preparation method of a solvent-free waterborne polyurethane resin, is characterized in that, carries out in the steps below:
(1) under 20-80 ℃, the amino-type cage-type silsesquioxane is joined in isocyanate-monomer, reaction is to limpid;
(2) add oxyethyl group terminated polymer glycol, wetting ability function monomer, dibasic alcohol and catalyzer di-n-butyltin dilaurate in (1) products therefrom, controlling the R value in the prepolymerization reaction process is 1.50-3.00, is warming up to 70-90 ℃ and continues to be down to room temperature after reaction 1-2h after 40-70 ℃ of reaction 1-2h;
(3) in (2) products therefrom, add neutralizing agent and water to be disperseed;
(4) add chainextender to carry out chain extending reaction 2-4h in 30-50 ℃, be down to room temperature, obtain aqueous polyurethane.
2. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that, the described amino-type cage-type silsesquioxane of step (1) is any one in following T8, T10, T12 or T14 structure:
R is-CH
2-CH
2-CH
2-NH
2.
3. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that, the described isocyanate-monomer of step (1) is tolylene diisocyanate, ditan-4,4-vulcabond, 1, hexamethylene-diisocyanate, isophorone diisocyanate, methylene radical-dicyclohexyl-4, a kind of in 4-vulcabond or Methylcyclohexyl diisocyanate.
4. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that, the described oxyethyl group terminated polymer of step (2) glycol is for having a kind of in following structure (I) or structure (II):
（Ⅰ）
（Ⅱ）
Wherein n is 1-1000.
5. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that, the described wetting ability function monomer of step (2) is dimethylol propionic acid, N methyldiethanol amine, N, N-dimethylethanolamine, N, N-dimethyl-ethylenediamine or N, a kind of in the N-diethyl ethylenediamine.
6. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that, the described dibasic alcohol of step (2) is polyether Glycols, polyester diol, polyester polyethers mixing dibasic alcohol, polyoxypropyleneglycol, polybutadiene diol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-tetrahydrochysene fluorine mutter glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-epsilon-caprolactone glycol or polycarbonate-1, a kind of in 6-hexylene glycol esterdiol.
7. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that, the described neutralizing agent of step (3) is a kind of in ammoniacal liquor or acetic acid.
8. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that, the described chainextender of step (4) is quadrol, 1,2-propylene diamine, 1,3-propylene diamine, Putriscine, 1, a kind of in 6-hexanediamine or Isosorbide-5-Nitrae-pentamethylene diamine.
9. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that, the mass ratio that adds amino-type cage-type silsesquioxane and isocyanate-monomer in step (1) is 1.384-2.775:1; The mass ratio that adds oxyethyl group terminated polymer glycol, wetting ability function monomer, dibasic alcohol and catalyzer di-n-butyltin dilaurate in step (2) is 22-32.7:114.94-183.48:8.81-12.88:1; It is 0.439-0.454:1 that step (3) adds the mass ratio of neutralizing agent and wetting ability function monomer; Adding the mass ratio of chainextender and oxyethyl group terminated polymer glycol in step (4) is 0.777-0.886:1.
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| CN104341572A (en) * | 2014-10-22 | 2015-02-11 | 江苏华夏制漆科技有限公司 | Preparation method of solvent-free water-based polyurethane resin |
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| CN104341572A (en) * | 2014-10-22 | 2015-02-11 | 江苏华夏制漆科技有限公司 | Preparation method of solvent-free water-based polyurethane resin |
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| CN113717371A (en) * | 2021-08-30 | 2021-11-30 | 山东一诺威新材料有限公司 | Preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and preparation method thereof |
| CN113717371B (en) * | 2021-08-30 | 2023-11-10 | 山东一诺威新材料有限公司 | Preparation method of low-viscosity reactive flame-retardant polyether polyol, reactive flame-retardant heat-conducting polyurethane electronic pouring sealant and preparation method thereof |
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