CN103467693A - Preparation method of waterborne polyurethane with excellent freeze-thawing stability - Google Patents
Preparation method of waterborne polyurethane with excellent freeze-thawing stability Download PDFInfo
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Abstract
The invention discloses a preparation method of waterborne polyurethane with excellent freeze-thawing stability. The preparation method specifically comprises the steps of: at 20-80 DEG C, adding amino type polyhedral oligomeric silsesquioxane into acetone of excessive isocyanate monomer, reacting to be clear, setting the temperature to be 60 DEG C, adding ethyoxyl-terminated polymer glycol, diol and polyol, and catalyst di-n-butyl tin dilaurate, reacting for one to two hours, and controlling the R value to be 1.50-3.00 in the prepolymerization reaction; then increasing the temperature to be 70-90 DEG C, continuously reacting for one to two hours, then cooling to room temperature, adding water for dispersion, adding a chain extender at 30-50 DEG C to conduct chain extension reaction for two to four hours, and cooling to room temperature to obtain waterborne polyurethane. Through tests, the waterborne polyurethane has favorable wear resistance property and bonding strength, as well as excellent freeze-thawing stability.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of preparation method with aqueous polyurethane of good freeze/thaw stability.
Background technology
Aqueous polyurethane is to take urethane resin as base-material, the novel high polymer material of water to replace organic solvent as dispersion medium of usining.It has not only retained some premium propertiess of conventional solvent type polyurethane, also have nontoxic, do not fire, the advantage such as free from environmental pollution and save energy, be subject to people's attention.As novel green material, in fields such as light textile, printing and dyeing, leather processing, wood working and buildings, be widely used at present.
Aqueous polyurethane combines the advantage of urethane with low VOC (VOC) content of water-based itself, meet " three the prerequisites " (resource that develops coatings industry, the energy, pollution-free) and " four E principles " (economic Economy, efficiency Efficiency, ecological Ecolo-gy, energy Energy) and the requirements of the times of day by day strengthening adapt.Water globe based polyurethane (WPU) technology has entered an important period, at present just towards future developments such as many kinds, multi-functional, low consumption, quality product matter, and is widely used in the closely bound up every field of living with people.
Self-emulsification is to introduce hydrophilic radical (mostly being the group that can form ionic linkage) in the molecular skeleton of urethane, then it is scattered in water and obtains aqueous polyurethane.Hydrophilic radical is to be present in the polyurethane molecular skeleton by hydrophilic monomer, makes polyurethane molecular have certain wetting ability, by hydrophilic radical emulsification urethane, makes aqueous polyurethane emulsion, and the aqueous polyurethane of the type is called self-emulsifying aqueous polyurethane.Self-emulsification can, by the hydrophilic radical in the proportioning reaction system and the different ratios of hydrophobic group, make polytype aqueous dispersion type and waterborne polyurethane.Adopt aqueous polyurethane that self-emulsification makes to there is dispersion particle diameters little, film-forming properties, the physicals such as adhesivity is good, stability is high, thereby develop very fastly, be the main method for preparing at present aqueous polyurethane.
Chen Zhi (CN101717489B) is used isocyanic ester 20-40, contains carboxy(l)polyester 20-40, chainextender 2-10, linking agent 1-3, neutralizing agent 3-10, epoxy resin 1-10, acetone 10-20, the preparation method comprise containing carboxy(l)polyester synthesize, get the raw materials ready, neutralization, chain extension and the emulsification of synthetic, the prepolymer of prepolymer, obtained self-emulsifying aqueous polyurethane.Polyester polyol, nano silicon and di-isocyanate reaction for Malaysian's chapter (CN102153984B), the performed polymer of generation-NCO end group; Adding hydrophilic chain extender and polyvalent alcohol monomer further reacts; Then with small molecules dibasic alcohol chain extension; With in triethylamine and conditioned reaction liquid to pH value 6-7, add the acetone that accounts for polyester polyol weight 5-40% to reduce the material viscosity, be dispersed into light blue translucent emulsion with deionized water; Last vacuum removal solvent acetone, obtain single-component high-heat-resistance aqueous polyurethane adhesive.
But not high, the viscosity of the present stage intensity of waterborne polyurethane resin and wear resistance are also good not, freeze thawing simultaneously is also poor, thereby also has been subject to certain restriction in its application facet.
Summary of the invention
The object of the invention is to provides a kind of preparation method with aqueous polyurethane of good freeze/thaw stability in order to overcome above the deficiencies in the prior art.
The present invention has following technique means to realize:
A kind of preparation method with aqueous polyurethane of good freeze/thaw stability, carry out in the steps below:
(1) under 20-80 ℃, the amino-type cage-type silsesquioxane is joined in the acetone soln of isocyanate-monomer, reaction is to limpid;
(2) add oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent 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, after 60 ℃ of reaction 1-2h, be warming up to 70-90 ℃ and continue to be down to room temperature after 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) adding water is disperseed in room temperature;
(4) in 30-50 ℃ add chainextender to carry out chain extending reaction 2-4h after, be down to room temperature, obtain aqueous polyurethane.
The described preparation method with aqueous polyurethane of good freeze/thaw stability, 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):
Wherein n is 1-1000.
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 polyvalent alcohol of step (2) can be in glycerol, tetramethylolmethane, TriMethylolPropane(TMP) or acrylate polyvalent alcohol a kind of.
The described chainextender of step (4) can be quadrol, 1,2-propylene diamine, 1,3-propylene diamine, Putriscine, 1, a kind of in 6-hexanediamine or Isosorbide-5-Nitrae-pentamethylene diamine.
The described preparation method with aqueous polyurethane of good freeze/thaw stability, wherein adding the mass ratio of amino-type cage-type silsesquioxane, isocyanate-monomer and acetone in step (1) is 1:1.58-2.52:6.82-10; The mass ratio that adds oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent alcohol and catalyzer di-n-butyltin dilaurate in step (2) is 20.2-33.9:67.8-107.8:1.24-1,7:1; Adding the mass ratio of chainextender and oxyethyl group terminated polymer glycol in step (3) is 0.397-0.41:1.
The invention provides a kind of waterborne polyurethane resin with good freeze/thaw stability of high combination property, 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 performed polymer building-up reactions together with oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent alcohol, while effectively avoiding amino-type cage-type silsesquioxane, dibasic alcohol and polyvalent alcohol and isocyanic ester direct 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) introduce the hydrophilic polymer glycol chains in the present invention in the urethane resin molecular side chain, improved the freeze-thaw stability that makes waterborne polyurethane resin.
Aqueous polyurethane provided by the invention is superior through the performance test properties, and wherein viscosity has dropped to below 36.1cp, and more than cohesive strength has reached 5.76MPa, wear resistance has reached below 0.45%, and the freeze-thaw stability number of times has reached more than 10 times.
Embodiment
Embodiment 1
(1) under 70 ℃, 88.00g amino-type cage-type silsesquioxane T8 is joined in acetone (750.00g) solution of the tolylene diisocyanate of 174.00g, reaction is to limpid.
(2) add wherein 2 of 75.00g, 2-dihydroxymethyl butoxy ethylene glycol (20EO, see structural formula (II), n=20 wherein) methyl ether (oxyethyl group terminated polymer glycol), the poly-dihydric alcohol 1000 of 200.00g, the glycerol of 4.60g and the catalyzer di-n-butyltin dilaurate of 2.71g, in 60 ℃ of reaction 2h; Then being warming up to 85 ℃ continues to be down to room temperature after reaction 2h.
(3) to the deionized water that adds 300g in the mixture of being down to after room temperature, in 25 ℃, disperseed.
(4) disperse after after 40 ℃ of quadrols that add 29.81g carry out chain extending reaction 3h, be down to room temperature, obtain having the aqueous polyurethane of good freeze/thaw stability.Its solid content is 33.35% after measured, and particle diameter is 323.6nm.
Embodiment 2-9 respectively walks reaction conditions and parameter in Table 1.
Reaction conditions and the parameter of table 1 embodiment 2-9 in each step
For the ease of carrying out Performance Ratio, the present invention has carried out building-up reactions according to the conventional synthetic method of aqueous polyurethane, and concrete grammar 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 25 ℃ of room temperatures 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 25 ℃ of room temperatures 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.
Aqueous polyurethane prepared by embodiments of the invention and Comparative Examples are carried out performance test, and what obtain the results are shown in Table 2.
Solid content and the particle diameter of the waterborne polyurethane resin made in table 2 embodiment 1-9
From above testing data, can significantly find out, the prepared aqueous polyurethane properties of the embodiment of the present invention obviously is better than Comparative Examples, wherein viscosity has dropped to below 36.1, cohesive strength has reached more than 5.76, wear resistance has reached below 0.45, the freeze-thaw stability number of times has reached more than 10 times, and not only physicals is superior, has good freeze-thaw stability simultaneously.
Claims (8)
1. the preparation method with aqueous polyurethane of good freeze/thaw stability, is characterized in that, carries out in the steps below:
(1) under 20-80 ℃, the amino-type cage-type silsesquioxane is joined in the acetone soln of isocyanate-monomer, reaction is to limpid;
(2) add oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent 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, after 60 ℃ of reaction 1-2h, be warming up to 70-90 ℃ and continue to be down to room temperature after reaction 1-2h;
(3) adding water is disperseed in room temperature;
(4) in 30-50 ℃ add chainextender to carry out chain extending reaction 2-4h after, be down to room temperature, obtain aqueous polyurethane.
2. the preparation method with aqueous polyurethane of good freeze/thaw stability 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 with aqueous polyurethane of good freeze/thaw stability 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 with aqueous polyurethane of good freeze/thaw stability 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 with aqueous polyurethane of good freeze/thaw stability 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.
6. the preparation method with aqueous polyurethane of good freeze/thaw stability according to claim 1, is characterized in that, the described polyvalent alcohol of step (2) is a kind of in glycerol, tetramethylolmethane, TriMethylolPropane(TMP) or acrylate polyvalent alcohol.
7. the preparation method with aqueous polyurethane of good freeze/thaw stability 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.
8. the preparation method with aqueous polyurethane of good freeze/thaw stability according to claim 1, it is characterized in that, the mass ratio that adds amino-type cage-type silsesquioxane, isocyanate-monomer and acetone in step (1) is 1:1.58-2.52:6.82-10; The mass ratio that adds oxyethyl group terminated polymer glycol, dibasic alcohol, polyvalent alcohol and catalyzer di-n-butyltin dilaurate in step (2) is 20.2-33.9:67.8-107.8:1.24-1,7:1; Adding the mass ratio of chainextender and oxyethyl group terminated polymer glycol in step (3) is 0.397-0.41:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263233A (en) * | 2014-10-22 | 2015-01-07 | 江苏华夏制漆科技有限公司 | Temporary protection paint combination based on modified polyurethane and preparing method thereof |
| CN107722221A (en) * | 2017-10-31 | 2018-02-23 | 湖南辰砾新材料有限公司 | A kind of composite foamed thermal insulation building material of alumina fibre POSS modified polyurethanes and preparation method thereof |
| CN108034349A (en) * | 2018-01-22 | 2018-05-15 | 南京理工大学 | The preparation method of the eight modified bi-component aqueous polyaminoester emulsions of nitro silsesquioxane |
| CN108192073A (en) * | 2017-12-23 | 2018-06-22 | 广东互典缓冲材料技术有限公司 | Padded coaming that a kind of wide temperature range domain uses and its preparation method and application |
| CN109535372A (en) * | 2018-10-31 | 2019-03-29 | 优美特（北京）环境材料科技股份公司 | A kind of aqueous polyurethane and preparation method thereof |
| CN109553746A (en) * | 2018-11-27 | 2019-04-02 | 射阳天源化工有限公司 | A kind of preparation method of four sulfydryls silsesquioxane modified aqueous polyurethane color fixing agent |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1791882A1 (en) * | 2004-09-24 | 2007-06-06 | Construction Research and Technology GmbH | Fluorine-modified reactive resin systems, method for producing them and their use |
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| WO2010106022A1 (en) * | 2009-03-16 | 2010-09-23 | Lamberti Spa | Hydrophilic comb polyurethane |
| CN102746505A (en) * | 2012-07-03 | 2012-10-24 | 山东省科学院新材料研究所 | Nonionic hydrophilic monomer for synthesis of waterborne polyurethane and synthetic method thereof |
| CN103265682A (en) * | 2013-05-22 | 2013-08-28 | 宜兴市华夏化工材料有限公司 | Special high-temperature resistant waterproof air and moisture permeable resin for coating printing and preparation method thereof |
-
2013
- 2013-09-25 CN CN201310441353.0A patent/CN103467693B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1791882A1 (en) * | 2004-09-24 | 2007-06-06 | Construction Research and Technology GmbH | Fluorine-modified reactive resin systems, method for producing them and their use |
| WO2010106022A1 (en) * | 2009-03-16 | 2010-09-23 | Lamberti Spa | Hydrophilic comb polyurethane |
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| CN102746505A (en) * | 2012-07-03 | 2012-10-24 | 山东省科学院新材料研究所 | Nonionic hydrophilic monomer for synthesis of waterborne polyurethane and synthetic method thereof |
| CN103265682A (en) * | 2013-05-22 | 2013-08-28 | 宜兴市华夏化工材料有限公司 | Special high-temperature resistant waterproof air and moisture permeable resin for coating printing and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| AJAYA K. NANDA等: "Nanostructured Polyurethane/POSS Hybrid Aqueous Dispersions Prepared by Homogeneous Solution Polymerization", 《MACROMOLECULES》, vol. 39, 31 December 2006 (2006-12-31) * |
| SAMY A. MADBOULY等: "Rheological Behavior of POSS/Polyurethane-Urea Nanocomposite Films Prepared by Homogeneous Solution Polymerization in Aqueous Dispersions", 《MACROMOLECULES》, vol. 40, 31 December 2007 (2007-12-31) * |
| 张其荣等: "POSS掺杂改性聚氨酯水性分散体乳液的研究", 《同济大学学报(自然科学版)》, vol. 37, no. 10, 15 October 2009 (2009-10-15) * |
| 陶玉仑等: "聚氨酯-纳米倍半硅氧烷杂化乳液的合成与表征", 《粘接》, vol. 29, no. 04, 15 April 2008 (2008-04-15) * |
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| CN104263233A (en) * | 2014-10-22 | 2015-01-07 | 江苏华夏制漆科技有限公司 | Temporary protection paint combination based on modified polyurethane and preparing method thereof |
| CN104263233B (en) * | 2014-10-22 | 2016-07-06 | 江苏华夏制漆科技有限公司 | A kind of temporary protective coating compositions based on modified polyurethane and preparation method thereof |
| CN107722221A (en) * | 2017-10-31 | 2018-02-23 | 湖南辰砾新材料有限公司 | A kind of composite foamed thermal insulation building material of alumina fibre POSS modified polyurethanes and preparation method thereof |
| CN108192073A (en) * | 2017-12-23 | 2018-06-22 | 广东互典缓冲材料技术有限公司 | Padded coaming that a kind of wide temperature range domain uses and its preparation method and application |
| CN108192073B (en) * | 2017-12-23 | 2021-05-07 | 广东互典缓冲材料技术有限公司 | Buffer material capable of being used in wide temperature range and preparation method and application thereof |
| CN108034349A (en) * | 2018-01-22 | 2018-05-15 | 南京理工大学 | The preparation method of the eight modified bi-component aqueous polyaminoester emulsions of nitro silsesquioxane |
| CN108034349B (en) * | 2018-01-22 | 2020-06-05 | 南京理工大学 | Preparation method of octanitrosilsesquioxane modified bi-component waterborne polyurethane emulsion |
| CN109535372A (en) * | 2018-10-31 | 2019-03-29 | 优美特（北京）环境材料科技股份公司 | A kind of aqueous polyurethane and preparation method thereof |
| CN109535372B (en) * | 2018-10-31 | 2021-08-27 | 优美特（北京）环境材料科技股份公司 | Waterborne polyurethane and preparation method thereof |
| CN109553746A (en) * | 2018-11-27 | 2019-04-02 | 射阳天源化工有限公司 | A kind of preparation method of four sulfydryls silsesquioxane modified aqueous polyurethane color fixing agent |
| CN109553746B (en) * | 2018-11-27 | 2020-12-11 | 射阳天源化工有限公司 | Preparation method of tetrasulfosilsesquioxane modified waterborne polyurethane color fixing agent |
| CN110684171A (en) * | 2019-10-29 | 2020-01-14 | 兰州科天水性高分子材料有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
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