CN104341572A - Preparation method of solvent-free water-based polyurethane resin - Google Patents
Preparation method of solvent-free water-based polyurethane resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of a solvent-free water-based polyurethane resin. The method comprises the following steps: uniformly mixing polyisocyanate, amino cage-type silsesquioxane, polyalcohol, ethoxy terminated polymer diol, hydrophilic functional monomer and a catalyst di-n-butyltin dilaurate, and carrying out prepolymerization reaction at 50-110 DEG C for 2-4 hours to obtain a polyurethane prepolymer; adding a neutralizer and water into the polyurethane prepolymer at room temperature, carrying out forced dispersion, adding a chain extender at 30-50 DEG C to carry out chain extension reaction for 2-4 hours, and cooling to room temperature to obtain the water-based polyurethane. The water-based polyurethane resin is solvent-free, and has the characteristic of zero VOC (volatile organic compound) discharge. The performance determination proves that the binding strength is 6.2 MPa above and optimally 6.5 MPa, the wear resistance is 0.87% below and optimally 0.65%, and the number of freezing times can be more than 10.
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 substitutes the emerging macromolecular material that organic solvent grows up, its special molecular structure and state of aggregation, make it have the performances such as excellent erosion resistant, snappiness, sticking power and chemical-resistant, the film good mechanical property that it is formed, 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 advantage of urethane combines with low VOC (VOC) content of water-based itself by aqueous polyurethane, meet " three prerequisites " (resource of development coatings industry, the energy, pollution-free) and " four E principles " (economic Economy, efficiency Efficiency, ecological Ecology, energy Energy) and the requirements of the times day by day strengthened adapt.Whole world aqueous polyurethane (WPU) technology has entered an important period, at present just towards future developments such as multi items, multi-functional, low consumption, quality product matter, and is widely used in living with people closely bound up every field.
The preparation method of aqueous polyurethane can be divided into outer emulsion process and self-emulsification two kinds.Outer emulsion process is also known as forced emulsification, and the method refers to and the base polyurethane prepolymer for use as of certain molecular weight or prepolymer solution are added emulsifying agent, under strong stirring, is scattered in water, makes corresponding polyaminoester emulsion or dispersion.This is the method preparing aqueous polyurethane in early days.The polyaminoester emulsion particle diameter prepared of outer emulsion process is comparatively large, and be generally greater than 0.1 μm, outward appearance gonorrhoea, stability in storage is poor, owing to using more emulsifying agent, makes the film-forming properties of product bad, and affects the water tolerance of glued membrane, intensity, toughness and cementability.Self-emulsification is also called internal emulsification method, is in the molecular skeleton of urethane, introduce hydrophilic radical (mostly being the group that can form ionic linkage), is then scattered in water and obtains aqueous polyurethane.Hydrophilic radical is present in polyurethane molecular skeleton by hydrophilic monomer, makes polyurethane molecular have certain wetting ability, and by hydrophilic radical emulsification urethane, obtained aqueous polyurethane emulsion, the aqueous polyurethane of the type is called self-emulsifying aqueous polyurethane.Self-emulsification by the different ratios of the hydrophilic radical in proportioning reaction system with hydrophobic group, can obtain polytype aqueous dispersion type and waterborne polyurethane.Adopt the obtained aqueous polyurethane of self-emulsification to have dispersion particle diameters little, the physicalies such as film-forming properties, adhesivity are good, stability is high, thus developing very fast, is the main method preparing aqueous polyurethane at present.
(CN102093533A and CN1511880A is that wetting ability function monomer obtains self-emulsifying cation type aqueous polyurethane with N methyldiethanol amine.
CN101717489B uses isocyanic ester 20 ~ 40, containing carboxy(l)polyester 20 ~ 40, chainextender 2 ~ 10, linking agent 1 ~ 3, neutralizing agent 3 ~ 10, epoxy resin 1 ~ 10, acetone 10 ~ 20, preparation method comprise synthesize containing carboxy(l)polyester, get the raw materials ready, the synthesis of prepolymer, the neutralization of prepolymer, chain extension and emulsification, obtain self-emulsifying aqueous polyurethane.
Modifier modification epoxy resin is obtained the epoxy resin of modification by CN100480349C, by polyisocyanates and polyester or polyether glycol reaction, then chainextender is added, obtain base polyurethane prepolymer for use as, use 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 water and to disperse with high speed dispersor, add neutralizing agent and linking agent, obtain modified aqueous adhesion agent of polyurethane.
CN102153984B polyester polyol, nano silicon and di-isocyanate reaction, generate the performed polymer of-NCO end group; Interpolation hydrophilic chain extender and monomeric polyol react further; Then with small molecules dibasic alcohol chain extension; With in triethylamine and regulate reaction solution to pH value 6 ~ 7, add the acetone accounting for polyester polyol weight 5 ~ 40% and reduce material viscosity, be dispersed into light blue translucent emulsion with deionized water; Last solvent removed by vacuum acetone, obtains single-component high-heat-resistance aqueous polyurethane adhesive.
The waterborne polyurethane resin preparation of present stage has two processes, first be the synthesis of hydrophilic prepolymer body, 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 the very important factor affecting product quality.In synthesis performed polymer process, system viscosity is high, can cause the uneven and heat transfer difficult of mixing of materials, be unfavorable for obtaining stable dispersion.For the viscosity problem of performed polymer, Traditional solutions adds a large amount of lower boiling organic solvent to help viscosity reduction, again with the method removing organic solvent vacuumized after obtaining product, the shortcoming of this kind of method consumes a large amount of organic solvent and the energy, part volatile organic solvent is remained in system, have certain pollution to environment, the product simultaneously prepared all has the shortcoming that intensity is not high, wear resistance is general, is therefore difficult to the needs meeting growing market.
Therefore how overcoming the deficiencies in the prior art is problems that current technical field of coatings needs solution badly.
Summary of the invention
Technical problem to be solved by this invention: need to add solvent in traditional urethane preparation process and regulate viscosity, be unfavorable for environment, proposes a kind of preparation method of solvent-free waterborne polyurethane resin.
Technical scheme:
A preparation method for solvent-free waterborne polyurethane resin, comprises the steps:
1st step, by weight, polyisocyanates 15 ~ 24 parts, amino-type cage-type silsesquioxane 0.2 ~ 1.7 part, polyvalent alcohol 2.4 ~ 9.8 parts, oxyethyl group terminated polymer glycol 1.7 ~ 10.2 parts, hydrophilic monomer 2.7 ~ 5.1 parts, catalyzer 0.01 ~ 0.5 part are mixed, prepolymerization reaction is carried out in intensification, obtains base polyurethane prepolymer for use as;
2nd step, in base polyurethane prepolymer for use as in adding neutralizing agent and 52.7 ~ 63.9 parts, water, be uniformly dispersed, then add chainextender 1.4 ~ 4.6 parts and carry out chain extending reaction, be down to room temperature, obtain aqueous polyurethane.
Described polyisocyanates is selected from tolylene diisocyanate, ditan-4,4-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, methylene radical-dicyclohexyl-4,4-vulcabond or Methylcyclohexyl diisocyanate.
Described amino cage-type silsesquioxane is that its three-dimensional arrangement is selected from T8, T10, T12 or T14 with aminopropyl trimethoxysilane or aminopropyl triethoxysilane for Material synthesis obtains.
Described polyvalent alcohol is selected from ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 1, 3-butyleneglycol, 1, 5-pentanediol, 1, 2-pentanediol, Diethylene Glycol, triethylene glycol, dipropylene glycol or tripropylene glycol, 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 is muttered glycol, poly-hexanodioic acid-1, 4-butanediol ester glycol, poly-epsilon-caprolactone glycol or polycarbonate-1, 6-hexylene glycol esterdiol.
Described hydrophilic monomer is selected from the one in dimethylol propionic acid, N methyldiethanol amine, N, N-dimethylethanolamine, N, N-dimethyl-ethylenediamine or N, N-diethyl ethylenediamine.
The structure of described oxyethyl group terminated polymer glycol is selected from the one in following formula (I) or formula (II):
Wherein, n is the arbitrary integer within 15 ~ 25.
The consumption of described oxyethyl group terminated polymer glycol is preferably 2 ~ 9 weight parts, more preferably 5 ~ 7 parts.
Described neutralizing agent is selected from acetic acid, hydrochloric acid, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
Described chainextender is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, Putriscine, 1,6-hexanediamine or Isosorbide-5-Nitrae-pentamethylene diamine.
Amino contained in the mole number of the isocyanate groups in isocyanate-monomer and the cage-type silsesquioxane of amino-type, polyvalent alcohol, oxyethyl group terminated polymer glycol, wetting ability function monomer and the total mole number ratio of hydroxyl are (1.5 ~ 3.0): 1.
Described catalyzer is di-n-butyltin dilaurate.
In the 1st described step, the temperature of prepolymerization reaction 50 ~ 110 DEG C, reaction times 2 ~ 4h.
In the 2nd described step, the temperature of chain extending reaction 30 ~ 50 DEG C, reaction times 2 ~ 4h.
Beneficial effect
The present invention by introducing the inorganic structure of 3 D stereo in urethane resin, while raising intensity, there is good wear resistance, additionally by adjustment formulation monomer component ratio, solve the problem easily occurring gel because the amino activity of cage-type silsesquioxane is high, have broad application prospects.
The invention provides a kind of waterborne polyurethane resin of high combination property, and there is following features:
(1) mixture containing amino cage-type silsesquioxane, polyvalent alcohol, oxyethyl group terminated polymer glycol, wetting ability function monomer is obtained prepolymer with polyisocyanates prepolymerization reaction by the present invention under the effect of catalyst dibutyltin cinnamic acid di-n-butyl tin, amino is compared hydroxyl and is had high reactive behavior, isocyanate-terminated compound can be formed faster than hydroxyl when prepolymerization reaction, technological operation is simple, and effectively avoids material viscosity too high.
(2) compared with traditional waterborne polyurethane, the present invention introduces 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, while 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, adopts the urethane resin using it as Material synthesis and embodies good wear resistance.
(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) in urethane resin molecular side chain, introduce hydrophilic polymer glycol chains in the present invention, improve the freeze-thaw stability of obtained waterborne polyurethane resin.
(7) in urethane resin molecule, introduce oxyethyl group terminated polymer glycol in the present invention, effectively can regulate the viscosity of urethane resin, make solvent-free urethane resin have relatively low viscosity.
(8) waterborne polyurethane resin that the present invention obtains is no-solvent type, has the feature of Diamond Search discharge.
Aqueous polyurethane in embodiment provided by the invention is through performance measurement, and cohesive strength reaches more than 6.2MPa, and optimal effectiveness reaches 6.5MPa, and wear resistance reaches less than 0.87%, and optimal effectiveness reaches 0.65%, and freezing can reach more than 10 times.
Embodiment
Embodiment 1 ~ 5
Raw material and the proportioning of following examples employing are as shown in table 1.
Table 1 embodiment 1 ~ 5 and comparative example 1 ~ 3 reaction conditions and parameter (unit: g)
Preparation method:
After polyisocyanates, amino-type cage-type silsesquioxane, polyvalent alcohol, oxyethyl group terminated polymer glycol, hydrophilic monomer, catalyst dibutyltin cinnamic acid di-n-butyl tin are mixed, carry out prepolymerization reaction 2 ~ 4h in 50 ~ 110 DEG C, obtain base polyurethane prepolymer for use as.Base polyurethane prepolymer for use as is added neutralizing agent under room temperature and water carries out Forced Dispersion, then add after chainextender carries out chain extending reaction 2 ~ 4h in 30 ~ 50 DEG C, be down to room temperature, obtain aqueous polyurethane.
Carry out performance test to the aqueous polyurethane that above embodiment and comparative example obtain, concrete outcome is in table 2.
The performance test results of resin in table 2 embodiment and comparative example
As can be seen from the above data, aqueous polyurethane provided by the invention is all greatly better than comparative example in viscosity, cohesive strength and wear resistance, shows that aqueous polyurethane provided by the invention has more superior physicals.
Embodiment 6
The consumption of oxyethyl group terminated polymer glycol is changed in the present embodiment.
A preparation method for solvent-free waterborne polyurethane resin, comprises the steps:
1st step, by tolylene diisocyanate 200g, aminopropyl cage type sesquialter siloxane T8 10g, ethylene glycol 50g part, 2,2-dihydroxymethyl butoxy ethylene glycol (20EO) methyl ether, dimethylol propionic acid 40g, catalyzer 1g mix, heat up 100 DEG C and carry out prepolymerization reaction/2h, obtain base polyurethane prepolymer for use as;
2nd step, in base polyurethane prepolymer for use as in adding ammoniacal liquor 1g and water 550g, be uniformly dispersed, then add Putriscine 20g and carry out chain extending reaction, temperature 50 C, time 3h, is down to room temperature, obtains aqueous polyurethane.
The performance data of the aqueous polyurethane prepared in this embodiment is as shown in table 3.
Performance data under the addition of the oxyethyl group terminated polymer that table 3 is different is same, add-on unit g
As can be seen from the table, by adjusting the consumption of oxyethyl group terminated polymer glycol, the problem of viscoelastic polyurethane knotting strength, freezing stability can be solved.
Embodiment 7
Adopt the polyisocyanates of Synolac modification in the present embodiment, the method for modification is: Oleum Gossypii semen 30g, glycerol 4g are mixed, and is warming up to 120 DEG C, add KOH catalyzer 0.1g, at 200 DEG C of reaction 2h, after cooling, then add phenylformic acid 3g, in 180 DEG C of reaction 2h, when being cooled to 40 DEG C, then add tolylene diisocyanate 30g and dimethylbenzene 20g, be warming up to 65 DEG C of insulation 2h, after being cooled to room temperature, filter and obtain the polyisocyanates of Synolac modification.Use it for the preparation of aqueous polyurethane.
1st step, by the tolylene diisocyanate 200g of Synolac modification, aminopropyl cage type sesquialter siloxane T8 10g, ethylene glycol 50g part, 2,2-dihydroxymethyl butoxy ethylene glycol (20EO) methyl ether 60g, dimethylol propionic acid 40g, catalyzer 1g mix, heat up 100 DEG C and carry out prepolymerization reaction/2h, obtain base polyurethane prepolymer for use as;
2nd step, in base polyurethane prepolymer for use as in adding ammoniacal liquor 1g and water 550g, be uniformly dispersed, then add Putriscine 20g and carry out chain extending reaction, temperature 50 C, time 3h, is down to room temperature, obtains aqueous polyurethane.Solid content 66.5%, particle diameter 177.2nm, viscosity 170.9cp, cohesive strength 7.2MPa, wear resistance 0.65%, freezing stability >10 time.Can find out, by by the tolylene diisocyanate of Synolac modification with after Synolac modification, cohesive strength and wear resistance can be improved.
Claims (10)
1. a preparation method for solvent-free waterborne polyurethane resin, is characterized in that, comprises the steps:
1st step, by weight, polyisocyanates 15 ~ 24 parts, amino-type cage-type silsesquioxane 0.2 ~ 1.7 part, polyvalent alcohol 2.4 ~ 9.8 parts, oxyethyl group terminated polymer glycol 1.7 ~ 10.2 parts, hydrophilic monomer 2.7 ~ 5.1 parts, catalyzer 0.01 ~ 0.5 part are mixed, prepolymerization reaction is carried out in intensification, obtains base polyurethane prepolymer for use as;
2nd step, in base polyurethane prepolymer for use as in adding neutralizing agent and 52.7 ~ 63.9 parts, water, be uniformly dispersed, then add chainextender 1.4 ~ 4.6 parts and carry out chain extending reaction, be down to room temperature, obtain aqueous polyurethane.
2. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that: described polyisocyanates is selected from tolylene diisocyanate, ditan-4,4-vulcabond, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, methylene radical-dicyclohexyl-4,4-vulcabond or Methylcyclohexyl diisocyanate.
3. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that: described amino cage-type silsesquioxane is that its three-dimensional arrangement is selected from T8, T10, T12 or T14 with aminopropyl trimethoxysilane or aminopropyl triethoxysilane for Material synthesis obtains.
4. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that: described polyvalent alcohol is selected from ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 1, 3-butyleneglycol, 1, 5-pentanediol, 1, 2-pentanediol, Diethylene Glycol, triethylene glycol, dipropylene glycol or tripropylene glycol, 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 is muttered glycol, poly-hexanodioic acid-1, 4-butanediol ester glycol, poly-epsilon-caprolactone glycol or polycarbonate-1, 6-hexylene glycol esterdiol.
5. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, it is characterized in that: described hydrophilic monomer is selected from dimethylol propionic acid, N methyldiethanol amine, N, one in N-dimethylethanolamine, N, N-dimethyl-ethylenediamine or N, N-diethyl ethylenediamine.
6. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that: the structure of described oxyethyl group terminated polymer glycol is selected from the one in following formula I or formula II:
(I)
(II)
Wherein, n is the arbitrary integer within 15 ~ 25; The consumption of described oxyethyl group terminated polymer glycol is 2 ~ 9 weight parts.
7. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that: described neutralizing agent is selected from acetic acid, hydrochloric acid, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
8. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that: described chainextender is selected from quadrol, 1,2-propylene diamine, 1,3-propylene diamine, Putriscine, 1,6-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: amino contained in the mole number of the isocyanate groups in isocyanate-monomer and the cage-type silsesquioxane of amino-type, polyvalent alcohol, oxyethyl group terminated polymer glycol, wetting ability function monomer and the total mole number ratio of hydroxyl are 1.5 ~ 3.0:1; Described catalyzer is di-n-butyltin dilaurate.
10. the preparation method of solvent-free waterborne polyurethane resin according to claim 1, is characterized in that: in the 1st described step, the temperature of prepolymerization reaction 50 ~ 110 DEG C, reaction times 2 ~ 4h; In the 2nd described step, the temperature of chain extending reaction 30 ~ 50 DEG C, reaction times 2 ~ 4h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105968295A (en) * | 2016-05-26 | 2016-09-28 | 湖南本安亚大新材料有限公司 | Waterborne polyurethane resin, waterborne polyurethane adhesive and preparation method thereof |
| CN108034033A (en) * | 2017-12-28 | 2018-05-15 | 长春市三化实业有限责任公司 | A kind of aqueous polyurethane emulsion and its non-solvent preparation |
| CN111793352A (en) * | 2020-07-07 | 2020-10-20 | 惠州大亚湾达志精细化工有限公司 | Waterborne polyurethane powder adhesive, elastic material and preparation method thereof |
| WO2021020194A1 (en) * | 2019-07-29 | 2021-02-04 | 株式会社Adeka | Urethane prepolymer, polyurethane, and powder dispersant comprising said polyurethane, and production method for urethane prepolymer and polyurethane |
| CN112898885A (en) * | 2020-11-03 | 2021-06-04 | 苏州恒祥环境工程有限公司 | Ceramic resin super-wear-resistant terrace and preparation method thereof |
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| CN102643416A (en) * | 2012-05-08 | 2012-08-22 | 合众（佛山）化工有限公司 | Isocyanate modified alkyd resin and preparation method thereof |
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| CN105968295B (en) * | 2016-05-26 | 2019-02-12 | 湖南本安亚大新材料有限公司 | A kind of waterborne polyurethane resin, water-based polyurethane adhesive and preparation method thereof |
| CN108034033A (en) * | 2017-12-28 | 2018-05-15 | 长春市三化实业有限责任公司 | A kind of aqueous polyurethane emulsion and its non-solvent preparation |
| WO2021020194A1 (en) * | 2019-07-29 | 2021-02-04 | 株式会社Adeka | Urethane prepolymer, polyurethane, and powder dispersant comprising said polyurethane, and production method for urethane prepolymer and polyurethane |
| CN111793352A (en) * | 2020-07-07 | 2020-10-20 | 惠州大亚湾达志精细化工有限公司 | Waterborne polyurethane powder adhesive, elastic material and preparation method thereof |
| CN112898885A (en) * | 2020-11-03 | 2021-06-04 | 苏州恒祥环境工程有限公司 | Ceramic resin super-wear-resistant terrace and preparation method thereof |
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