CN103467693B - A kind of preparation method of the aqueous polyurethane with good freeze/thaw stability - Google Patents
A kind of preparation method of the aqueous polyurethane with good freeze/thaw stability Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the aqueous polyurethane with good freeze/thaw stability, be specially: at 20-80 DEG C, amino-type cage-type silsesquioxane is joined in the acetone soln of excess isocyanate monomer, after reaction is extremely limpid, it is 60 DEG C by Temperature Setting, add wherein ethyoxyl terminated polymer glycol, dihydroxylic alcohols, polyalcohol and catalyst di-n-butyltin dilaurate, reaction 1-2h, controls R value for 1.50-3.00 in prepolymerization reaction process; Then be warming up to 70-90 DEG C and continue reaction and be down to room temperature after 1-2h, then add water and disperse wherein, then add chain extender to carry out, after chain extending reaction 2-4h, being down to room temperature in 30-50 DEG C, obtain aqueous polyurethane. Aqueous polyurethane provided by the invention has good wearability and adhesion strength after tested, has good freeze-thaw stability simultaneously.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of aqueous polyurethane with good freeze/thaw stabilityPreparation method.
Background technology
Aqueous polyurethane is the novel high score taking polyurethane resin as base-material, using water to replace organic solvent as decentralized mediumSub-material. It has not only retained some premium properties of conventional solvent type polyurethane, also have nontoxic, do not fire, free from environmental pollutionAnd save the advantages such as the energy, be subject to people's attention. As novel green material, add at light textile, printing and dyeing, leather at presentThe fields such as work, timber processing and building are widely used.
Aqueous polyurethane is tied the advantage of polyurethane and low VOC (VOC) content of water-based itself mutuallyClose, meet " three prerequisites " (resource, the energy, pollution-free) and " four E principles " (economic Economy, efficiency of development coatings industryEfficiency, ecological Ecolo-gy, energy Energy) and the requirements of the times of strengthening day by day 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 be widely used in the closely bound up every field of living with people.
Self-emulsification is in the molecular skeleton of polyurethane, to introduce hydrophilic radical (mostly being the group that can form ionic bond),Then be scattered in and in water, obtained aqueous polyurethane. Hydrophilic radical is to be present in polyurethane molecular bone by hydrophilic monomerFrame, makes polyurethane molecular have certain hydrophily, by hydrophilic radical emulsification polyurethane, makes aqueous polyurethane emulsion, shouldThe aqueous polyurethane of type is called self-emulsifying aqueous polyurethane. Self-emulsification can be by the hydrophily in proportioning reaction systemThe different proportion of group and hydrophobic group, makes polytype water-dispersion type and waterborne polyurethane. Adopt self-emulsificationIt is little that the aqueous polyurethane making has dispersion particle diameters, film forming, the physical property such as adhesiveness is good, stability is high, thereby developmentVery fast, be the main method of preparing at present aqueous polyurethane.
Chen Zhi (CN101717489B) uses isocyanates 20-40, contains carboxyl polyester 20-40, chain extender 2-10, crosslinking agent1-3, nertralizer 3-10, epoxy resin 1-10, acetone 10-20, preparation method comprise containing carboxyl polyester synthesize, get the raw materials ready, prepolymerNeutralization, chain extension and the emulsification of synthetic, prepolymer, obtained self-emulsifying aqueous polyurethane. Malaysian's chapter (CN102153984B)With PEPA, nano silicon and di-isocyanate reaction, the performed polymer of generation-NCO end group; Add hydrophilic chain extenderAnd polyalcohol monomer further reacts; Then with little molecule dihydroxylic alcohols chain extension; With in triethylamine and regulate reactant liquor to pH value 6-7, add the acetone that accounts for PEPA weight 5-40% to reduce material viscosity, be dispersed into light blue translucent breast by deionized waterLiquid; Last vacuum removal solvent acetone, obtains single-component high-heat-resistance aqueous polyurethane adhesive.
But not high, the viscosity of the present stage intensity of waterborne polyurethane resin and wearability are also good not, freeze thawing simultaneously alsoPoor, thereby be also subject to certain restriction in its application aspect.
Summary of the invention
The object of the invention is to provide in order to overcome above the deficiencies in the prior art one to there is good freeze/thaw stableThe preparation method of the aqueous polyurethane of property.
The present invention has following technological means to realize:
There is a preparation method for the aqueous polyurethane of good freeze/thaw stability, carry out in the steps below:
(1) at 20-80 DEG C, amino-type cage-type silsesquioxane is joined in the acetone soln of isocyanate-monomer,Reaction is to limpid;
(2) to adding ethyoxyl terminated polymer glycol, dihydroxylic alcohols, polyalcohol and catalyst February in (1) products therefromCinnamic acid di-n-butyl tin, controls R value for 1.50-3.00 in prepolymerization reaction process, after 60 DEG C of reaction 1-2h, be warming up to 70-90 DEG CContinue to be down to room temperature after reaction 1-2h; In the molal quantity that above-mentioned R value refers in system total NCO group and system always OH group moleThe ratio of number;
(3) add water and disperse in room temperature;
(4) add chain extender to carry out, after chain extending reaction 2-4h, being down to room temperature in 30-50 DEG C, obtain aqueous polyurethane;
Wherein the described amino-type cage-type silsesquioxane of step (1) can be in following T8, T10, T12 or T14 structureAny one:
R is-CH2-CH2-CH2-NH2。
The described isocyanate-monomer of step (1) can be toluene di-isocyanate(TDI), diphenyl methane-4,4-bis-isocyanic acidsEster, 1, hexamethylene-diisocyanate, IPDI, methylene-dicyclohexyl-4,4-vulcabond or methyl ringOne in hexyl diisocyanate.
The described ethyoxyl terminated polymer glycol of step (2) can be for to have in following structure (I) or structure (II)A kind of:
Wherein n is 1-1000.
The described dihydroxylic alcohols of step (2) can be polyester polyethers mixing dihydroxylic alcohols, polyoxypropyleneglycol, polybutadiene twoAlcohol, polyethylene glycol adipate glycol, poly-adipic acid-1,6-hexylene glycol esterdiol, polytetrahydrofuran diol, poly-adipic acid-1,4-butanediol ester glycol, poly-epsilon-caprolactone glycol or Merlon-1, the one in 6-hexylene glycol esterdiol.
The described polyalcohol of step (2) can be glycerine, pentaerythrite, trimethylolpropane or acrylate polyalcoholIn one.
The described chain extender of step (4) can be ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, Putriscine, 1,6-One in hexamethylene diamine or Isosorbide-5-Nitrae-pentanediamine.
The preparation method of the described aqueous polyurethane with good freeze/thaw stability, wherein adds amino in step (1)The mass ratio of type cage-type silsesquioxane, isocyanate-monomer and acetone is 1: 1.58-2.52: 6.82-10; In step (2)Add the mass ratio of ethyoxyl terminated polymer glycol, dihydroxylic alcohols, polyalcohol and catalyst di-n-butyltin dilaurate to be20.2-33.9: 67.8-107.8: 1.24-1,7: 1; In step (4), add the matter of chain extender and ethyoxyl terminated polymer glycolAmount is than being 0.397-0.41: 1.
The waterborne polyurethane resin with good freeze/thaw stability that the invention provides a kind of high combination property, has as followsFeature:
(1) the present invention first will contain amino-type cage-type silsesquioxane carry out isocyanate-terminated after, seal with ethyoxylEnd polymer diol, dihydroxylic alcohols, polyalcohol carry out performed polymer synthetic reaction together, effectively avoid amino-type cage model sesquialter silicaWhen alkane, dihydroxylic alcohols and polyalcohol directly react with isocyanates, because of the amino active high gelation that occurs.
(2), compared with traditional aqueous polyurethane, the present invention introduces cage in the molecular structure main chain of waterborne polyurethane resinType silsesquioxane molecular structure, is embedded in inorganic molecular structure in organic molecular structure, obtains the poly-of inorganic hybridizationAmmonia ester resin, in not affecting the good characteristic of resin own, especially can improve the compatibility of resin and inorganic substrate and glueKnot power.
(3) cage-type silsesquioxane has the molecular structure of high functionality, for polyurethane laminate provides high strength.
(4) cage-type silsesquioxane has high hardness, adopts and uses it as the synthetic polyurethane resin embodiment of raw material betterWearability.
(5) there is the cage silsesquioxane structure of 3-D solid structure, play the conduct that nanometer strengthens, improve polyurethaneComprehensive physical performance.
(6) in the present invention, in polyurethane resin molecular side chain, introduce hydrophilic polymer glycol chains, improved and made water-basedThe freeze-thaw stability of polyurethane resin.
Aqueous polyurethane provided by the invention is superior through performance test properties, its medium viscosity dropped to 36.1cp withUnder, more than adhesion strength has reached 5.76MPa, wearability has reached below 0.45%, and freeze-thaw stability number of times has reached 10 timesAbove.
Detailed description of the invention
Embodiment 1
(1), at 70 DEG C, 88.00g amino-type cage-type silsesquioxane T8 is joined to the toluene diisocynate of 174.00gIn acetone (750.00g) solution of ester, reaction is to limpid.
(2) add wherein 2 of 75.00g, (20EO is shown in structural formula (II), wherein n to 2-dihydroxymethyl butoxy ethylene glycol=20) glycerine of the poly-dihydric alcohol 1000 of methyl ether (ethyoxyl terminated polymer glycol), 200.00g, 4.60g and 2.71gCatalyst di-n-butyltin dilaurate, in 60 DEG C of reaction 2h; Then being warming up to 85 DEG C continues to be down to room temperature after reaction 2h.
(3) disperse in 25 DEG C to the deionized water that adds 300g in the mixture of being down to after room temperature.
(4) add the ethylenediamine of 29.81g to carry out, after chain extending reaction 3h, being down to room temperature in 40 DEG C after disperseing, obtain having goodThe aqueous polyurethane of good freeze-thaw stability. Its solid content is 33.35% after measured, and particle diameter is 323.6nm.
Each step reaction condition of embodiment 2-9 and parameter are in table 1.
Reaction condition 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 synthetic anti-according to the conventional synthetic method of aqueous polyurethaneShould, concrete grammar is as follows:
Comparative example 1
At 70 DEG C, by 8.03g propane diols, 360.00g cetomacrogol 1000,4.00g glycerine, 61.40g trihydroxy methylThe acetone of propionic acid, 395.52g IPDI, 1.57g di-n-butyltin dilaurate and 740.00g, is heated toAfter 60 DEG C of reaction 2h, be warming up to 80 DEG C and continue to be down to 25 DEG C of room temperatures after reaction 2h, obtain base polyurethane prepolymer for use as; At 25 DEG C, in advanceIn aggressiveness, add 32.96g ammoniacal liquor, then add 720.00g deionized water to disperse 5min. Add 26.94g's in 40 DEG C againEthylenediamine carries out, after chain extending reaction 3h, being down to room temperature, obtains aqueous polyurethane.
Comparative example 2
At 70 DEG C, by 8.03g propane diols, 360.00g cetomacrogol 1000,4.00g glycerine, 60.16g trihydroxy methylThe acetone of propionic acid, 380.00g toluene di-isocyanate(TDI), 1.46g di-n-butyltin dilaurate and 650.00g, is heated to 60 DEG CAfter reaction 2h, be warming up to 80 DEG C and continue to be down to 25 DEG C of room temperatures after reaction 2h, obtain base polyurethane prepolymer for use as; At 25 DEG C, to performed polymerIn add 32.29g ammoniacal liquor, then add 670.00g deionized water to disperse 5min. Again in 40 DEG C of second two that add 39.29gAmine carries out, after chain extending reaction 3h, being down to room temperature, obtains aqueous polyurethane.
Aqueous polyurethane prepared by embodiments of the invention and comparative example 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 making in table 2 embodiment 1-9
Can significantly find out from above test data, the prepared aqueous polyurethane properties of the embodiment of the present invention is brightAobvious be better than comparative example, its medium viscosity has dropped to below 36.1, and adhesion strength has reached more than 5.76, wearability reached 0.45 withUnder, freeze-thaw stability number of times has reached more than 10 times, and not only physical property is superior, has good freeze-thaw stability simultaneously.
Claims (7)
1. a preparation method with the aqueous polyurethane of good freeze/thaw stability, is characterized in that, carries out in the steps below:
(1), at 20-80 DEG C, amino-type cage-type silsesquioxane is joined in the acetone soln of isocyanate-monomer to reactionTo limpid;
(2) in (1) products therefrom, add ethyoxyl terminated polymer glycol, dihydroxylic alcohols, polyalcohol and catalyst two laurateDi-n-butyl tin, controls R value for 1.50-3.00 in prepolymerization reaction process, after 60 DEG C of reaction 1-2h, be warming up to 70-90 DEG C of continuationAfter reaction 1-2h, be down to room temperature;
(3) add water and disperse in room temperature;
(4) add chain extender to carry out, after chain extending reaction 2-4h, being down to room temperature in 30-50 DEG C, obtain aqueous polyurethane;
Wherein the described amino-type cage-type silsesquioxane of step (1) is any one in following T8, T10, T12 or T14 structureKind:
R is-CH2-CH2-CH2-NH2。
2. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, is characterized in that,The described isocyanate-monomer of step (1) is toluene di-isocyanate(TDI), diphenyl methane-4,4-vulcabond, 1,6-oneself twoIsocyanates, IPDI, methylene-dicyclohexyl-4,4-vulcabond or methylcyclohexyl two isocyanidesOne in acid esters.
3. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, is characterized in that,The described ethyoxyl terminated polymer glycol of step (2) is the one having in following structure (I) or structure (II):
(I)
(II)
Wherein n is 1-1000.
4. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, is characterized in that,The described dihydroxylic alcohols of step (2) is polyester polyethers mixing dihydroxylic alcohols, polyoxypropyleneglycol, polybutadiene diol, poly-adipic acidGlycol ester glycol, poly-adipic acid-1,6-hexylene glycol esterdiol, polytetrahydrofuran diol, poly-adipic acid-BDO ester twoAlcohol, poly-epsilon-caprolactone glycol or Merlon-1, the one in 6-hexylene glycol esterdiol.
5. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, is characterized in that,The described polyalcohol of step (2) is the one in glycerine, pentaerythrite, trimethylolpropane or acrylate polyalcohol.
6. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, is characterized in that,The described chain extender of step (4) is ethylenediamine, 1,2-propane diamine, 1, and 3-propane diamine, Putriscine, 1,6-hexamethylene diamine or Isosorbide-5-Nitrae-One in pentanediamine.
7. the preparation method of the aqueous polyurethane with good freeze/thaw stability according to claim 1, 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; In step (2), add ethyoxyl terminated polymer glycol, dihydroxylic alcohols, polyalcohol and the positive fourth of catalyst two laurate twoThe mass ratio of base tin is 20.2-33.9:67.8-107.8:1.24-1.7:1; In step (4), add chain extender and ethyoxyl end-blockingThe mass ratio of polymer diol is 0.397-0.41:1.
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| 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 |
| 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 |
| CN108034349B (en) * | 2018-01-22 | 2020-06-05 | 南京理工大学 | Preparation method of octanitrosilsesquioxane modified bi-component waterborne polyurethane emulsion |
| 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 |
| 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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