CN101885829A - Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof - Google Patents
Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an alcohol end capping nonionic polyurethane cross-linking agent and a preparation method and application thereof. The preparation method particularly comprises the following steps of: performing an addition reaction of 100 parts of diisocyanate, 20 to 50 parts of nonionic hydrophilic monomer and 5 to 20 parts of polyhydric alcohol in a reactor based on the mole ratio; and then capping free isocyanate radicals by adding 45 to 160 parts of alcohol end-capping agent to obtain the alcohol end capping nonionic polyurethane cross-linking agent. The cross-linking agent prepared by the invention can be mixed with water in any ratio and has the advantages of high storage stability at a higher temperature, a lower temperature and room temperature, convenient use and high performance; the cross-linking agent can be used for aqueous emulsion of polymer prepared by polymerizing polyurethane or free radicals, and particularly for water-based paints and water-based adhesives; besides, the cross-linking agent can be also used for improving mechanical properties of polyhydroxy polymer-containing materials.
Description
Technical field
The invention belongs to the polyurethane cross-linking agent field, relate to a kind ofly specifically, also relate to the preparation method and the application of this linking agent in addition by alcohol end capping nonionic polyurethane cross-linking agent.
Background technology
As the important source material-isocyanate-monomer of synthesis of polyurethane and related products, because himself NCO group and nucleophilic reagent have high reaction activity and high, make this system very active at normal temperatures, can't exist with the single component form; In addition, NCO group in the isocyanic ester and water vigorous reaction, but it is as coating or other products, when using as raw materials such as tamanoris, the moisture that contains in synthetic polyurethane coating and the tamanori damp atmosphere to moisture in the raw materials such as solvent, resin, pigment and working-yard can be very responsive, brought a lot of troubles for the application of products such as polyurethane coating and tamanori.If can make isocyanate groups at room temperature to the reaction inactivation of reactive hydrogen, so just can coexist an individual system and needn't worry the influence of water with the aqueous polyurethane that contains reactive hydrogen to it, water content in the resin of solvent, pigment and reactive hydrogen is required also can descend, improved stable the time, also can eliminate the murder by poisoning that causes because of the remaining isocyanate monomer, the masked isocyanate system is exactly a fine method that can effectively address the above problem.
Nowadays, along with the raising of social development and people's environmental consciousness, particularly countries in the world mechanism of environmental protection organization has higher requirement to the quantity discharged of organic solvent now, makes water-borne coatings and aqueous adhesive become the focus of current research gradually.But the poorly water-soluble of present most of water-borne coatings and aqueous adhesive, and its over-all properties especially solvent resistance compare with the solvent-borne type glue paste with solvent based coating with water tolerance or have a certain distance.Therefore how improving the performance of water-borne coatings and aqueous adhesive, make it can replace solvents type coating and solvent-based adhesive, be the problem that the research and development person of this respect extremely pays close attention to.
The at present independent linear water-borne coatings and the various performances of aqueous adhesive all are subjected to great restriction, especially it is relatively poor in the performance of mechanics mechanical properties, and therefore improving the crosslinked ability of polyurethanes aqueous adhesive is the importance that the needs in using afterwards improve.Crosslinked and external crosslinking was two kinds in now the means that polyurethane aqueous binding agent is improved crosslinked ability mainly contained.In crosslinked be that selection by raw material makes lightly crosslinked emulsion, external crosslinking is to add linking agent before use in emulsion, is equivalent to two component systems.The interior crosslinked restriction that mainly has degree of crosslinking at present, therefore by contrast, the emulsion property that external crosslinking makes is better, and can be by changing the consumption of linking agent, the performance that adjusting is filmed.But there is the problem of lacking working life and needing before use to prepare in the employed linking agent of external crosslinking method at present.
Closed isocyanate crosslinker is that isocyanate groups is by the prepared product of end-capping reagent end-blocking.By sealing, can make single-component product.Under certain temperature and other conditions, crosslinking reaction takes place in the isocyanate groups regeneration in the sealing urethane, generates heat-curable urethane.The method of sealing and corresponding encapsulant all have bigger influence to the deblocking effect in Blocking of Isocyanates effect and the use.Various encapsulants commonly used now respectively have relative merits to the sealing effect of isocyanate groups (NCO), are easy to make the NCO sealing as phenol compound, but sealing product dissociation temperature is higher, and in use need consider the problem of free phenol environmental pollution; Oximes also is easy to make the NCO sealing, but costs an arm and a leg, and when using the aldoxime class to make encapsulant, also can have problems such as free aldehyde environmental pollution in addition.Phenols and oximes end-capping reagent all can not obtain watersoluble closed isocyanic ester sealing monomer, and the solvent-borne type closed isocyanic ester monomer has considerable influence because of using a large amount of solvents to environment, has not met the developing direction of contemporary society's " greenization ".
Summary of the invention
The objective of the invention is to avoid the shortcomings and deficiencies of above-mentioned prior art, a kind of shelf-stable and alcohol end capping nonionic polyurethane cross-linking agent easy to use be provided, and this linking agent can stable dispersion in water.
Another object of the present invention is to provide the preparation method who obtains above-mentioned linking agent.
The present invention passes through vulcabond, the non-ionic hydrophilic monomer, and polyvalent alcohol and alcohol end capping agent are reacted under the effect of solvent and catalyzer, and the NCO group is sealed by end-capping reagent fully in the linking agent that finally obtains.The linking agent that obtains has good water dispersible and stability in storage, the linking agent of preparation directly can be joined coating in addition, in solidifying agent and the aqueous polyurethane emulsion, obtain having the water-borne coatings of premium properties, aqueous adhesive and high-strength polyurethane resin, thereby the purposes of realization linking agent of the present invention.
The present invention is achieved by the following technical programs:
A kind of alcohol end capping nonionic polyurethane cross-linking agent is characterized in that, is formed and is obtained by addition reaction by following raw material:
By mole number, 100 parts of vulcabond, 20～50 parts of non-ionic hydrophilic monomers, 5～20 parts of polyvalent alcohols, 45～160 parts of end-capping reagents; Described polyvalent alcohol is trivalent alcohol, tetravalent alcohol or pentavalent alcohol.
Described vulcabond is one or more the mixture in aliphatic diisocyanate, alicyclic diisocyanate and the aromatic diisocyanate.
Described aliphatic diisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, decamethylene vulcabond or ten dimethylene diisocyanates; Wherein, preferred hexamethylene diisocyanate.
Described alicyclic diisocyanate is 1,2-vulcabond hexanaphthene, 1,3-vulcabond hexanaphthene, 1,4-vulcabond hexanaphthene or isophorone diisocyanate; Wherein, preferred isophorone diisocyanate.
Described aromatic diisocyanate is a 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or 4,4-vulcabond ditan; Wherein, preferred 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or 4,4-vulcabond ditan.
Described non-ionic hydrophilic monomer is at least a in polyoxyethylene glycol, poly glycol monomethyl ether, polyoxyethylene glycol monobutyl ether and the polypropylene glycol; Wherein, preferred polyoxyethylene glycol or polypropylene glycol.
Described end-capping reagent is one or more mixtures in trifluoroethanol, ethapon, 2-Ethylhexyl Alcohol, hexalin, propyl carbinol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the 2-ethyl hexyl oxy ethanol; Wherein, preferred ethylene glycol monoethyl ether or ethylene glycol monobutyl ether.
Described trivalent alcohol is at least a in trimethylolethane, TriMethylolPropane(TMP), glycerine, trolamine, trimethylolpropane trimethacrylate, Viscoat 295 and the trihydroxymethyl propane, preferred TriMethylolPropane(TMP) glycerine.
Described tetravalent alcohol is a tetramethylolmethane.
Described pentavalent alcohol is an Xylitol.
The preparation method of above-mentioned alcohol end capping nonionic polyurethane cross-linking agent specifically may further comprise the steps:
By mole number, 20～50 parts of non-ionic hydrophilic monomers, 5～20 parts of 100 parts of vulcabond and polyvalent alcohols, under the effect of organic solvent, under 40～80 ℃, carry out addition reaction, (the NCO content value the when numerical value that the NCO content that records and Theoretical Calculation are come out in the reaction is suitable when reaching the calculated value of NCO group content, method for measuring is a Di-n-Butyl Amine residual titration method), under 60～90 ℃, add the alcohol end capping agent and continue reaction for 45～160 parts, when detecting no NCO group, be cooled to room temperature (25 ± 10 ℃), stirring following (about 1500rpm) adds water and disperses, and obtains alcohol end capping nonionic polyurethane cross-linking agent.
Described organic solvent can be hydrophilic solvent such as acetone, butanone, methylethylketone, N-Methyl pyrrolidone etc., also can be hydrophobic nature solvent such as toluene etc., preferred acetone, methylethylketone, N-Methyl pyrrolidone.
In order to shorten the reaction times, described addition reaction also adds the organic tin catalyzer, and described catalyzer can be organic tin catalyzer, tertiary amine catalyst and organo-metallic class catalyzer; Preferred dibutyl tin laurate or stannous octoate.Catalyst consumption be the mixture that constitutes of non-ionic hydrophilic monomer, vulcabond and polyvalent alcohol total mass 0～0.2% (promptly 0～0.2wt%).
The alcohol end capping nonionic polyurethane cross-linking agent of method for preparing can be used for water-borne coatings, aqueous binder, contains the natural of active hydroxyl and synthetic polymkeric substance.
The reaction expression of above-mentioned reaction is as follows:
BH: end-capping reagent
OCN-Ar-NCO: vulcabond
T
b: end-blocking temperature (60～90 ℃)
T
d: deblocking temperature (100～150 ℃)
HO-R-OH: contain active hydroxy polymer.
The present invention has following advantage and effect with respect to prior art:
(1) the prepared aqueous polyurethane linking agent of the present invention is than traditional solvent-borne type linking agent environment-protecting asepsis, be fit to current " greenization " growth requirement more, and using raw material is the technical grade product that is easy to get, the preparation condition gentleness, and technology is simple and good repeatability arranged.
(2) the prepared polyurethane cross-linking agent of the present invention can be miscible with arbitrary proportion with water, and the water dispersion that obtains has good thermostability and freeze-thaw stability (to be placed in 100 ℃ the baking oven, taking out behind the 24h does not have the gel caking to occur, and proves that its heat-resistant stability is good; Be placed in 0 ℃ the refrigerator-freezer freezingly, take out at room temperature behind the 24h and melt, no precipitate gel is lumpd, and proves that its freeze-thaw stability is good); In addition, the water dispersion that obtains has the shelf lives (place and surpasses 1 year, the gel-free caking phenomenon at shady and cool place) that surpasses 1 year at normal temperatures.Overcome level of response of the prior art and be difficult to control, preparation poor repeatability, poorly water-soluble, the defective of poor storage stability.
(3) alcohol end capping nonionic polyurethane cross-linking agent of the present invention can make the degree of crosslinking of own or its cross-linking system have excellent controllability (amount of isocyanic ester or polyvalent alcohol in the adjustment raw material), can effectively improve mechanical property, particularly tensile property behind the emulsion film forming; Therefore can be widely used in the linking agent of the water and milk of the polymkeric substance that urethane or radical polymerization makes, especially for the linking agent of water-borne coatings and aqueous adhesive; This linking agent mechanical property of also can be used for containing the synthetic base polymer material (as poly(lactic acid), polycaprolactone etc.) of active hydroxyl is improved in addition.
Description of drawings
Fig. 1 is the infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of embodiment 1 preparation.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
With 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.05mol PEG1000 (cetomacrogol 1000), 0.02mol TMP (TriMethylolPropane(TMP)), (20 is 1ml for 25ml acetone and 2, being 0.2wt%) stannous octoate adds in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, at 40 ℃ of reaction 6h down; Be warming up to 60 ℃, add the 0.045mol ethylene glycol monoethyl ether, react 5 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 25 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH6.7, viscosity 185Cps.The infrared spectrum of alcohol end capping nonionic polyurethane cross-linking agent of preparation is referring to Fig. 1,2250～2270cm of this infrared spectrum
-1The place does not have the charateristic avsorption band of NCO group, illustrates that end-blocking is complete.
Embodiment 2
With 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.02mol PEG1000 (cetomacrogol 1000), 0.005mol TMP (TriMethylolPropane(TMP)), (20 is 1ml for 20ml butanone and 2, being 0.2wt%) sour inferior tin adds agitator is housed, in the four-hole round-bottomed flask of the 250ml of airway, condenser, at 80 ℃ of reaction 3h down; Be warming up to 90 ℃, add the 0.16mol ethylene glycol monoethyl ether, react 2 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 20 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH7.3, viscosity 160Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 3
With 0.1mol IPDI (isophorone diisocyanate), 0.04mol PPG1000 (polypropylene glycol 1000), 0.01mol glycerine, (20 is 1ml for 15ml N-Methyl pyrrolidone and 2, being 0.2wt%) dibutyl tin laurate adds in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, at 60 ℃ of reaction 5h down; Be warming up to 80 ℃, add the 0.1mol ethylene glycol monobutyl ether, react 3 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 30 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH6.1, viscosity 140Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 4
With 0.1mol TDI (2, the 4-tolylene diisocyanate), 0.04mol PPG1000 (polypropylene glycol 1000), 0.01mol TMP (TriMethylolPropane(TMP)), (20 is 1m1 for 15mlN-methyl-2-pyrrolidone and 1, being 0.1wt%) dibutyl tin laurate adds in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, at 60 ℃ of reaction 5h down; Be warming up to 80 ℃, add the 0.1mol ethylene glycol monobutyl ether, react 3 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 25 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH6.9, viscosity 165Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 5
With 0.1mol MDI (4,4-vulcabond ditan), 0.04mol PEG1000 (cetomacrogol 1000), 0.01mol glycerine, (20 is 1ml for 15ml N-Methyl pyrrolidone and 2, being 0.2wt%) dibutyl tin laurate adds in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, at 60 ℃ of reaction 4h down; Be warming up to 80 ℃, add the 0.1mol ethylene glycol monoethyl ether, react 3 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 20 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH7.1, viscosity 170Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 6
With 0.1mol HDI (hexamethylene diisocyanate), 0.05mol PEG1000 (cetomacrogol 1000), 0.02mol TMP (TriMethylolPropane(TMP)), 20ml butanone and 2 (0.2wt%) stannous octoates add in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, react 6h down at 40 ℃; Be warming up to 80 ℃, add the 0.045mol ethylene glycol monoethyl ether, react 4 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 25 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH6.2, viscosity 140Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 7
With 0.1mol HDI (hexamethylene diisocyanate), 0.04mol PPG1000 (polypropylene glycol 1000), 0.01mol TMP (TriMethylolPropane(TMP)), 15ml N-Methyl pyrrolidone and 2 (0.2wt%) dibutyl tin laurates add in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, react 5h down at 60 ℃; Be warming up to 80 ℃, add the 0.1mol ethylene glycol monobutyl ether, react 4 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 20 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH6.3, viscosity 155Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 8
With 0.1mol decamethylene vulcabond, 0.08mol poly glycol monomethyl ether, 0.01mol trimethylolethane and 15ml methylethylketone add in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, react 5h down at 8 ℃; Be warming up to 80 ℃, add 0.1mol ring ethanol, react 4 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 25 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH7.1, viscosity 150Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
Embodiment 9
With 0.1mol 2, the 6-tolylene diisocyanate, 0.10mol polyoxyethylene glycol monobutyl ether, 0.015mol tetramethylolmethane, 15ml toluene and 2 (0.2wt%) dibutyl tin laurates add in the four-hole round-bottomed flask of the 250ml that agitator, airway, condenser are housed, react 5h down at 60 ℃; Be warming up to 80 ℃, add the 0.045mol trifluoroethanol, react 4 hours to the NCO group fully by end-blocking, through infrared detection, at 2250～2270cm
-1The place does not have the charateristic avsorption band of NCO group; Be cooled to 25 degree, add water under 1500rpm stirs and disperse, obtain the alcohol end capping nonionic polyurethane cross-linking agent water dispersion, be light yellow transparent thickness liquid state.Solid content is 30%, PH7.5, viscosity 188Cps.The infrared spectrum of the alcohol end capping nonionic polyurethane cross-linking agent of preparation and Fig. 1 are approximate.
End-blocking based polyurethane linking agent with the above embodiment of the present invention preparation, join polyaminoester emulsion (solid content 30%, PH7.0) and in the hydroxyl-terminated polylactic acid (Mn=12 ten thousand), dissolving mechanical blending in the appropriate solvent (chloroform or methylene dichloride), make the blended liquid of stable uniform, wherein Zhi Bei linking agent accounts for 1% of system total mass, and film forming also will obtain film and be positioned over baking 0.5h in 120 ℃ of baking ovens under the room temperature.Relatively the baking before with the baking after changes of mechanical properties, specifically see Table 1～9.
Table 1a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 1 linking agent
Table 1b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 1 linking agent
Table 2a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 2 linking agents
Table 2b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 2 linking agents
Table 3a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 3 linking agents
Table 3b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 3 linking agents
Table 4a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 4 linking agents
Table 4b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 4 linking agents
Table 5a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 5 linking agents
Table 5b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 5 linking agents
Table 6a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 6 linking agents
Table 6b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 6 linking agents
Table 7a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 7 linking agents
Table 7b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 7 linking agents
Table 8a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 8 linking agents
Table 8b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 8 linking agents
Table 9a contains polyurethane film changes of mechanical properties before and after 120 ℃ of bakings of embodiment 9 linking agents
Table 9b contains polylactic acid membrane changes of mechanical properties before and after 120 ℃ of bakings of embodiment 9 linking agents
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of an alcohol end capping nonionic polyurethane cross-linking agent is characterized in that, may further comprise the steps:
By mole number, 5～20 parts of 20～50 parts of non-ionic hydrophilic monomers, 100 parts of vulcabond and polyvalent alcohols, under the effect of organic solvent, under 40～80 ℃, carry out addition reaction, when reaching the calculated value of NCO group content, under 60～90 ℃, add the alcohol end capping agent and continue reaction for 45～160 parts, when detecting no NCO group, be cooled to 15～35 ℃, add water under stirring and disperse, obtain alcohol end capping nonionic polyurethane cross-linking agent; Described polyvalent alcohol is trivalent alcohol, tetravalent alcohol or pentavalent alcohol.
2. preparation method according to claim 1 is characterized in that:
Also add the organic tin catalyzer in the described addition reaction, described organic tin catalyzer is stannous octoate or dibutyl tin laurate, and its consumption is 0～0.2% of the mixture total mass that constitutes of non-ionic hydrophilic monomer, vulcabond and polyvalent alcohol.
3. preparation method according to claim 1 and 2 is characterized in that:
Described vulcabond is one or more the mixture in aliphatic diisocyanate, alicyclic diisocyanate and the aromatic diisocyanate;
Described non-ionic hydrophilic monomer is at least a in polyoxyethylene glycol, poly glycol monomethyl ether, polyoxyethylene glycol monobutyl ether and the polypropylene glycol;
Described end-capping reagent is one or more mixtures in trifluoroethanol, ethapon, 2-Ethylhexyl Alcohol, hexalin, propyl carbinol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the 2-ethyl hexyl oxy ethanol;
Described trivalent alcohol is at least a in trimethylolethane, TriMethylolPropane(TMP), glycerine, trolamine, trimethylolpropane trimethacrylate, Viscoat 295 and the trihydroxymethyl propane;
Described tetravalent alcohol is a tetramethylolmethane;
Described pentavalent alcohol is an Xylitol.
4. preparation method according to claim 3 is characterized in that:
Described aliphatic diisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates, decamethylene vulcabond or ten dimethylene diisocyanates;
Described alicyclic diisocyanate is 1,2-vulcabond hexanaphthene, 1,3-vulcabond hexanaphthene, 1,4-vulcabond hexanaphthene or isophorone diisocyanate;
Described aromatic diisocyanate is a 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate or 4,4-vulcabond ditan.
5. preparation method according to claim 4 is characterized in that:
Described aliphatic diisocyanate is a hexamethylene diisocyanate;
Described alicyclic diisocyanate is an isophorone diisocyanate;
Described aromatic diisocyanate is a 2,4 toluene diisocyanate.
6. preparation method according to claim 3 is characterized in that:
Described trivalent alcohol is TriMethylolPropane(TMP), trimethylolethane or glycerine.
7. preparation method according to claim 3 is characterized in that:
Described end-capping reagent is ethylene glycol monoethyl ether or ethylene glycol monobutyl ether;
Described non-ionic hydrophilic monomer is polyoxyethylene glycol or polypropylene glycol.
8. preparation method according to claim 1 is characterized in that:
Described organic solvent is acetone, butanone, methylethylketone, N-Methyl pyrrolidone or toluene.
9. an alcohol end capping nonionic polyurethane cross-linking agent is characterized in that, it is by any described preparation method's preparation of claim 1～8.
10. the application of the described alcohol end capping nonionic polyurethane cross-linking agent of claim 9 is characterized in that: described linking agent is used for water-borne coatings, aqueous binder, contains the synthetic base polymer material of active hydroxyl.
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| CN102167798A (en) * | 2011-03-14 | 2011-08-31 | 惠州市长润发涂料有限公司 | Waterborne polyurethane curing agent and waterborne polyurethane dispersoid |
| CN102337073A (en) * | 2011-08-18 | 2012-02-01 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
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Cited By (34)
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| CN102167798B (en) * | 2011-03-14 | 2012-07-04 | 惠州市长润发涂料有限公司 | Waterborne polyurethane curing agent and waterborne polyurethane dispersoid |
| CN102167798A (en) * | 2011-03-14 | 2011-08-31 | 惠州市长润发涂料有限公司 | Waterborne polyurethane curing agent and waterborne polyurethane dispersoid |
| CN102337073B (en) * | 2011-08-18 | 2013-12-25 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
| CN102337073A (en) * | 2011-08-18 | 2012-02-01 | 中科院广州化学有限公司 | Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof |
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| US10815351B2 (en) | 2012-03-30 | 2020-10-27 | Evonik Operations Gmbh | Polyurethane foam production process, pre-mix, formulation, and product |
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| KR20140143429A (en) * | 2012-03-30 | 2014-12-16 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Polyurethane foam production process, pre-mix, formulation, and product |
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| CN103289054A (en) * | 2013-05-30 | 2013-09-11 | 长春工业大学 | Xylitol aromatic polyurethane |
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| CN105732952B (en) * | 2016-03-21 | 2019-03-08 | 黄山联固新材料科技有限公司 | A kind of high modulus nonionic waterborne polyurethane and preparation method thereof |
| CN105732952A (en) * | 2016-03-21 | 2016-07-06 | 黄山联固新材料科技有限公司 | High-modulus nonionic water-based polyurethane and preparation method thereof |
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