CN110343234A - A kind of quick-drying water dispersed isocyanate curing agent composition and its preparation - Google Patents
A kind of quick-drying water dispersed isocyanate curing agent composition and its preparation Download PDFInfo
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- CN110343234A CN110343234A CN201910666023.9A CN201910666023A CN110343234A CN 110343234 A CN110343234 A CN 110343234A CN 201910666023 A CN201910666023 A CN 201910666023A CN 110343234 A CN110343234 A CN 110343234A
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to isocyanate curing agent technical field, a kind of quick-drying water dispersed isocyanate curing agent composition and preparation method thereof is disclosed.Quick-drying water dispersed isocyanate curing agent composition of the invention, including following two part: the aliphatic polyisocyante part of the hydrophilic modifying of 50-95 mass parts；The aromatic polyisocyanate part of the non-hydrophilic modification of 5-50 mass parts.After emulsifying in water-based system, the aromatic polyisocyanate part of non-hydrophilic modification can keep the longer up time by the aliphatic polyisocyante portion envelops of hydrophilic modifying in water phase；And after coating application moisture evaporation, rate of drying is greatly improved, while realizing rapid draing, there is the long up time；Effectively solution hydrophilic modifying aromatic polyisocyanate rate of drying is fast but the up time is extremely short, and the aliphatic of hydrophilic modifying the more cured with isocyanates speed is slow and causes using limited problem.
Description
Technical field
The invention belongs to isocyanate curing agent technical field, in particular to a kind of quick-drying water-dispersion type isocyanic acid
Ester curing agent composition and preparation method thereof.
Background technique
Currently, aqueous double-component polyurethane largely uses in the field that solvent-based two-component polyurethane is covered, success
Be applied to the industries such as water-based industrial paint, woodcare paint, floor paint.Aqueous double-component polyurethane has good Physical Mechanical
Can, can match in excellence or beauty solvent type dual-component polyurethane on gloss, hardness, chemical-resistant, and due to the low solvent of water-based system
Content, relative solvent system has very big advantage in environmental protection.But the curing rate of aqueous double-component polyurethane coating
It is much slower than solvent-based two-component polyurethane coating, this seriously constrains the further genralrlization of aqueous double-component polyurethane coating.This
It is since in solvent-based two-component polyurethane coating, aromatic polyisocyanates (mainly TDI or MDI type) curing agent is obtained
It, can be with since aromatic polyisocyanates reactivity is high to being widely used, and in aqueous double-component polyurethane coating
Water vigorous reaction, the up time is extremely short, so the aliphatic polyisocyante that can only often use reactivity much lower is (main
If HDI or IPDI type), thus rate of drying has a long way to go with solvent type.
Patent US3996154, US4433095 uses polyalkylene glycol monoalkyl ether as hydrophilic component to TDI or MDI type isocyanide
Acid esters is modified, and has obtained the emulsifiable isocyanate component of water.But the Hydrophilic polyisocyanates meeting of this method synthesis
With water fast reaction, in water-based system gel quickly, the up time is extremely short, therefore fresh in aqueous double-component polyurethane coating
There is application.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of rapid draing
Water dispersed isocyanate curing agent composition.
Another object of the present invention is to provide a kind of above-mentioned quick-drying water dispersed isocyanate curing agent composition
Preparation method.
The purpose of the present invention is realized by following proposal:
A kind of quick-drying water dispersed isocyanate curing agent composition, including following two part: 50-95 mass
The aliphatic polyisocyante part (A) of the hydrophilic modifying of part；The aromatic series polyisocyanic acid of the non-hydrophilic modification of 5-50 mass parts
Ester moiety (B).
The NCO average functionality > 2.5 of the aliphatic polyisocyante part (A) of the hydrophilic modifying, preferably > 3.
The aliphatic polyisocyante part (A) of the hydrophilic modifying is by including aliphatic polyisocyante (C) and parent
Water modifying agent (D) reaction obtains.
The mass parts of aliphatic polyisocyante (C) used and hydrophilic modifier (D) are preferably 50-90 mass parts, 0.5-
20 mass parts.
The condition of the reaction preferably reacts 2-8h in 60-120 DEG C of heating.
The reaction preferably carries out under solvent (E) environment, and the dosage of the solvent (E) is preferably 0-40 mass parts.
The solvent (E) be ethers, esters, hydro carbons equal solvent without the active hydrogen reacted with isocyanates, especially
Preferably propylene glycol methyl ether acetate, diethyl malonate, Propylene Glycol Dimethyl Ether etc..
The aliphatic polyisocyante (C) can be tripolymer, biuret, the urea diketone types of aliphatic isocyanates
At least one of polyisocyanates, preferably at least one of the polyisocyanates of HDI, IPDI.
The hydrophilic modifier (D) can be non-ionic hydrophilic modifying agent (D1) or ionic hydrophilic modifier (D2).
The non-ionic hydrophilic modifying agent (D1) can be polyalkylene glycol monoalkyl ether and polyethylene glycol propylene glycol list alkane
At least one of base ether；Molecular weight is preferably 200-2000, more preferably 300-1000；Its structural formula such as following formula (one)
It is shown:
Wherein, R1The alkyl of linear chain or branched chain within preferably C10, such as methyl, ethyl, isopropyl, butyl, preferably
For methyl.
The ionic hydrophilic modifier (D2) be by containing amino or hydroxyl sulfonic acid (D2-1) and tertiary amine (D2-2) it is anti-
The salt that should be obtained；Wherein, the molar ratio of sulfonic acid (D2-1) and tertiary amine (D2-2) containing amino or hydroxyl can be 1:0.8-1:1.5,
Preferably 1:1.
The condition of the reaction is conventional reaction condition.
Shown in the molecular formula such as following formula (two) of the sulfonic acid (D2-1) containing amino or hydroxyl:
HO-R2-SO3H or R4-HN-R2-SO3H
(2)
Wherein, R2For the substituted or unsubstituted alkyl of divalent, R4For H or substituted or unsubstituted straight chain, the branch of monovalence
Or cricoid alkyl.
The tertiary amine (D2-2) is the trialkylamine without hydroxyl or amino group, such as triethylamine, tri-isopropyl amine, three fourths
Base amine, diisopropylethylamine, N, N- dimethyl cyclohexyl amine etc..
The aromatic polyisocyanate part (B) of the non-hydrophilic modification may include the different containing aromatic series of 50-100 mass parts
The polyisocyanates (F) of cyanic acid ester structure and the solvent (G) of 0-50 mass parts.
Without parents such as polyethers, carboxylic acid, sulfonic acid in the structure of the polyisocyanates (F) of the structure containing aromatic isocyanate
Water-bound；Its NCO average functionality > 2.0, preferably > 2.5；It can be aromatic polyisocyanate (F1) or aromatic series isocyanic acid
The polyisocyanates (F2) that ester is obtained with aliphatic isocyanates mixing copolyreaction, the class of aromatic isocyanate (F1 and F2)
Type is preferably TDI, MDI type, particularly preferably TDI type.
The solvent (G) be ethers, esters, hydro carbons equal solvent without the active hydrogen reacted with isocyanates, it is especially excellent
It is selected as propylene glycol methyl ether acetate, diethyl malonate, Propylene Glycol Dimethyl Ether, ethyl acetate, butyl acetate etc..
The present invention also provides a kind of preparation method of above-mentioned quick-drying water dispersed isocyanate curing agent composition,
By the way that the aliphatic polyisocyante part (A) of hydrophilic modifying for including 50-95 mass parts, the non-hydrophilic of 5-50 mass parts are changed
Property aromatic polyisocyanate part (B) be uniformly mixed obtain.
Quick-drying water dispersed isocyanate curing agent composition of the invention, preparation method is simple, and composition is easy
In being dispersed in water, when being used for aqueous double-component polyurethane coating with the water-base resin of hydroxyl there is rate of drying to be exceedingly fast, can
Using the advantage that the time is long, obtained coating is water-fast, excellent chemical resistance.
Quick-drying water dispersed isocyanate curing agent composition of the invention includes the aliphatic of hydrophilic modifying
The aromatic polyisocyanate part (B) of polyisocyanate part (A) and non-hydrophilic modification, it is non-after being emulsified in water-based system
It the aromatic polyisocyanate part (B) of hydrophilic modifying, can be by the aliphatic polyisocyanate cyanogen of hydrophilic modifying due to there is no hydrophilic radical
Acid ester moiety (A) is wrapped up, so the aromatic polyisocyanate part (B) of non-hydrophilic modification and water and hydroxy resin occur instead
The chance answered greatly reduces, and aliphatic polyisocyante part (A) reactivity of the hydrophilic modifying of shell is low, thus in water
Xiang Zhongke is kept for the longer up time.And after coating application moisture volatilizees substantially, the non-hydrophilic modification of high reaction activity
Aromatic polyisocyanate part can be spread with polyol resin compatible, thus rate of drying is greatly improved, it is quick realizing
While dry, there is the long up time.Although it is fast effectively to solve hydrophilic modifying aromatic polyisocyanate rate of drying
It is more, but react and be exceedingly fast with water, in water-based system gel quickly, the up time is extremely short, and the aliphatic of hydrophilic modifying is more
Polyisocyanates curing rate is slow and causes using limited problem.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material involved in the following example can be obtained from commercial channel.
Embodiment 1
Poly glycol monomethyl ether (500 molecular weight, Jiangsu Province Hai'an petrochemical industry) 10.54 mass parts are heated to 100-110 DEG C
Vacuumize 2h, be cooled to 60 DEG C, be added Desmodur N 3300 (solvent-free HDI trimer is created in Cohan, NCO content is 21.8 ±
0.3%) 29.74 mass parts of 49.18 mass parts and propylene glycol methyl ether acetate, rise to 100 DEG C for temperature after adding, and at this
At a temperature of the reaction was continued 4h.It is cooled to room temperature, adding Desmodur IL BA, (TDI tripolymer is created in Cohan, and 51% contains admittedly, NCO content
For 8.0%) 10.54 mass parts, the isocyanate curing agent composition that 65% obtained after mixing evenly contains admittedly is faint yellow
Prescribed liquid, measuring nco value is 10.7%, and (25 DEG C) of viscosity are 300cps.
Embodiment 2
By polyethylene glycol polypropylene glycol monobutyl ether, (trade name LB 25 is created in 2250 molecular weight, Cohan, polyethylene glycol/poly- the third two
Alcohol segment ratio is heated to 100-110 DEG C and vacuumizes 2h for 12.43 mass parts of 75:25), is cooled to 60 DEG C, and Desmodur is added
(solvent-free HDI trimer is created in Cohan, and NCO content is 21.8 ± 0.3%) 54.94 mass parts of N 3300 and propylene glycol monomethyl ether vinegar
27.40 mass parts of acid esters, rise to 100 DEG C for temperature after adding, and the reaction was continued at such a temperature 4h.It is cooled to room temperature, adds
Desmodur IL BA (TDI tripolymer is created in Cohan, and 51% contains admittedly, NCO content 8.0%) 5.23 mass parts, after mixing evenly
The isocyanate curing agent composition that 70% obtained contains admittedly is light yellow transparent liquid, and measuring nco value is 12.2%, viscosity
(25 DEG C) are 350cps.
Embodiment 3
By polyethylene glycol polypropylene glycol monobutyl ether, (trade name LB 25 is created in 2250 molecular weight, Cohan, polyethylene glycol/poly- the third two
Alcohol segment ratio is heated to 100-110 DEG C and vacuumizes 2h for 10.78 mass parts of 75:25), is cooled to 60 DEG C, and Desmodur is added
(solvent-free HDI trimer is created in Cohan, and NCO content is 21.8 ± 0.3%) 47.67 mass parts of N 3300 and propylene glycol monomethyl ether vinegar
18.84 mass parts of acid esters, rise to 100 DEG C for temperature after adding, and the reaction was continued at such a temperature 4h.It is cooled to room temperature, adds
Desmodur IL BA (TDI tripolymer is created in Cohan, and 51% contains admittedly, NCO content 8.0%) 22.70 mass parts, after mixing evenly
The isocyanate curing agent composition that 70% obtained contains admittedly is light yellow transparent liquid, and measuring nco value is 12.0%, viscosity
(25 DEG C) are 400cps.
Embodiment 4
By polyethylene glycol polypropylene glycol monobutyl ether, (trade name LB 25 is created in 2250 molecular weight, Cohan, polyethylene glycol/poly- the third two
Alcohol segment ratio is heated to 100-110 DEG C and vacuumizes 2h for 8.64 mass parts of 75:25), is cooled to 60 DEG C, and Desmodur N is added
3300 (solvent-free HDI trimer is created in Cohan, and NCO content is 21.8 ± 0.3%) 38.18 mass parts and propylene glycol monomethyl ether acetic acid
7.73 mass parts of ester, rise to 100 DEG C for temperature after adding, and the reaction was continued at such a temperature 4h.It is cooled to room temperature, adds
Desmodur IL BA (TDI tripolymer is created in Cohan, and 51% contains admittedly, NCO content 8.0%) 45.45 mass parts, after mixing evenly
The isocyanate curing agent composition that 70% obtained contains admittedly is light yellow transparent liquid, and measuring nco value is 11.8%, viscosity
(25 DEG C) are 500cps.
Embodiment 5
The synthesis of amino-containing sulfonic acid (D2-1): by 122.1 mass parts of 1,3- propane sultone (1.0 molar part) and ring penta
85.2 mass parts of amine (1.0 molar part) and the mixing of 1000 mass parts ethyl alcohol, and it is heated to 60-65 DEG C of heat preservation 4h, it is cooled to 5-
15 DEG C are overnight, have a large amount of white solids to be precipitated, with ethanol washing solid and drying, obtain 163.0 mass parts white solid powders,
As hydrophilic modifier 3- (cyclopentamine) -1- propane sulfonic acid.
By Desmodur N 3900 (solvent-free HDI trimer is created in Cohan, and NCO content is 23.5 ± 0.3%) 58.45 matter
Measure part, 2.34 mass parts of 3- (cyclopentamine) -1- propane sulfonic acid of above-mentioned synthesis, 1.46 mass parts of diisopropylethylamine, propylene glycol first
The mixing of 23.96 mass parts of ether acetate, rises to 100 DEG C for temperature after adding, insulation reaction 5h.It is cooled to room temperature, adds
Desmodur L67MPA/X (Cohan creates TDI and sums it up object, and 67% contains admittedly, NCO content 11.9%) 13.79 mass parts, stirring are equal
The isocyanate curing agent composition that 70% obtained after even contains admittedly is light yellow transparent liquid, and measuring nco value is 14.9%, is glued
(25 DEG C) of degree are 250cps.
Embodiment 6
By Desmodur N 3300 (solvent-free HDI trimer is created in Cohan, and NCO content is 21.8 ± 0.3%) 36.24 matter
Measure part, Desmodur Z 4470MPA/X (TDI tripolymer is created in Cohan, and 70% contains admittedly, NCO content 11.9%) 18.12 mass
Part, 1.99 mass parts of 2- isethionic acid, 1.60 mass parts of triethylamine, the mixing of 27.54 mass parts of propylene-glycol diacetate will be warm
Degree rises to 100 DEG C, insulation reaction 5h.Be cooled to room temperature, add Desmodur HL BA (Cohan create TDI/HDI mixed trimer,
60% contains admittedly, NCO content 10.5%) 65% isocyanate curing agent contained admittedly that obtains after mixing of 14.50 mass parts
Composition is light yellow transparent liquid, and measuring nco value is 10.9%, and (25 DEG C) of viscosity are 500cps.
Comparative example 7
By poly glycol monomethyl ether (500 molecular weight, Jiangsu Province Hai'an petrochemical industry) 10.54 mass parts, it is heated to 100-110 DEG C
Vacuumize 2h.Be cooled to 60 DEG C, be added Desmodur N 3300 (solvent-free HDI trimer is created in Cohan, NCO content is 21.8 ±
0.3%) 49.18 mass parts, 29.74 mass parts of propylene glycol methyl ether acetate, Desmodur IL BA (TDI tripolymer is created in Cohan,
51% contains admittedly, NCO content 8.0%) temperature rises to 100 DEG C after adding by 10.54 mass parts, insulation reaction 4h.It is cooled to
Room temperature, the isocyanate curing agent composition that 65% obtained after mixing evenly contains admittedly are light yellow transparent liquid, measure nco value
It is 10.6%, (25 DEG C) of viscosity are 350cps.
Performance test
The isocyanate curing agent composition that above-described embodiment is prepared and the nonionic isocyanates of commercialization are consolidated
Agent Cohan wound Bayhydur 3100 (nco value 17.4%) compares.Wherein, the hydroxyl third of two commercialization has been selected
Olefin(e) acid resin: lotion PA-4816 (hat will new material, hydroxy radical content 3.2%, admittedly containing 38%), acrylic acid secondary breakup body PA-
4842 (hat will new material, hydroxy radical content 3.3%, admittedly it is prepared according to the following formulation containing 42%) with above-mentioned isocyanate curing agent
At aqueous double-component polyurethane coating.
1 hydroxy component formula of table
| Specific reagent | Mass percent | Component | Producer |
| PA-4816 or PA-4842 | 80 | Water-based hydroxyl resin | It is preced with will new material |
| Tego-902W | 0.2 | Deaeration agent | Digao |
| BYK-333 | 0.4 | Levelling agent | Bi Ke chemistry |
| BYK-024 | 0.3 | Defoaming agent | Aerochemistry |
| Hydropalat-140 | 0.4 | Wetting agent | Corning |
| DPnB | 2 | Coalescing agent | DOW Chemical |
| DPM | 3 | Coalescing agent | DOW Chemical |
| OS-8W | 0.3 | Thickener | It is preced with will |
| OS-2020 | 0.4 | Thickener | It is preced with will |
| Pure water | 13 |
Isocyanate component: the curing agent in above-described embodiment is divided with curing agent Bayhydur 3100 as a comparison
60% is not diluted to admittedly containing spare with PMA.
Wherein, the ratio of hydroxy component and isocyanate component is calculated by NCO/OH=1.5.Hydroxy component and isocyanide
After the mixing of acid esters component, then appropriate viscosity is adjusted to water and is constructed.Execution conditions are as follows: 25 DEG C, humidity 60%, wet-film thickness
It is 80 μm.Test hardness and patience are carried out after coating air drying 7 days, pencil hardness test standard is GB/T 6739-
2006, water resistance test standard is GB/T 23999-2009, and alcohol resistance testing standard is GB/T 23999-2009, test result
It is as shown in table 2 below:
2 polyurethane coating performance parameter of table
| Tack-free times | Up time | Pencil hardness | Water resistance | Alcohol resistance | |
| Embodiment 1/PA-4816 | 1h10min | 6h | H | Pass through | Pass through |
| Embodiment 2/PA-4816 | 1h50min | 7h | F | Pass through | Pass through |
| Embodiment 3/PA-4816 | 45min | 6h | H | Pass through | Pass through |
| Embodiment 4/PA-4816 | 30min | 4h | H | Pass through | Pass through |
| Embodiment 5/PA-4816 | 1h30min | 6h | H | Pass through | Pass through |
| Embodiment 6/PA-4816 | 1h | 7h | 2H | Pass through | Pass through |
| Comparative example 7/PA-4816 | 1h | 2h | H | Pass through | Pass through |
| Bayhydur 3100/PA-4816 | 3h | 6h | F | Pass through | Pass through |
| Embodiment 1/PA-4842 | 2h15min | 4h | F | Pass through | Pass through |
| Comparative example 7/PA-4842 | 2h10min | 1h | F | Pass through | Pass through |
| Bayhydur 3100/PA-4842 | 5h | 4h | HB | Pass through | Pass through |
The above results show nonionic curing dose of Bayhydur 3100 of the commercialization relative to standard, and the present invention is implemented
The coating that the curing agent composition of example is prepared shows the tack-free times of much shorter, it means that rate of drying obtains
To significantly improving, and kept for the excellent up time.And although comparative example 7 shows shorter tack-free times,
But the up time greatly shortens.This is because in embodiment 7, after aliphatic isocyanates and aromatic isocyanate mixing
Reacted with hydrophilic radical, since aromatic isocyanate reactivity is higher, the ratio reacted with hydrophilic modifier also faster,
In water-based system emulsify after aromatic isocyanate be in hydrophilic shell, it is bigger with the catalytic chance of water phase, with water and
The reaction meeting of hydroxy resin so that the up time it is shorter.And in curing agent composition of the invention, aromatic isocyanate does not have
Have by hydrophilic modifying, aromatic isocyanate is in the stratum nucleare of hydrophobic after emulsifying in water-based system, by the fat of hydrophilic modifying
The package protection of race's isocyanates emulsion layer, thus much smaller with the catalytic chance of water phase, so show it is very long can
Excellent hardness and water-fast, alcohol resistance energy are shown using the time, and based on its solid layer being prepared, is highly suitable for
In aqueous double-component polyurethane coating.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of quick-drying water dispersed isocyanate curing agent composition, it is characterised in that including following two part:
The aliphatic polyisocyante part of the hydrophilic modifying of 50-95 mass parts；The aromatic series of the non-hydrophilic modification of 5-50 mass parts is more
Isocyanate moiety.
2. quick-drying water dispersed isocyanate curing agent composition according to claim 1, it is characterised in that: institute
The aliphatic polyisocyante part for the hydrophilic modifying stated is by including that aliphatic polyisocyante and hydrophilic modifier react to obtain.
3. quick-drying water dispersed isocyanate curing agent composition according to claim 2, it is characterised in that: institute
Mass parts with aliphatic polyisocyante and hydrophilic modifier are 50-99 mass parts, 0.5-20 mass parts；The item of the reaction
Part is to react 2-8h in 60-120 DEG C of heating.
4. quick-drying water dispersed isocyanate curing agent composition according to claim 2, it is characterised in that: institute
The aliphatic polyisocyante stated is in the tripolymer, biuret, urea diketone types polyisocyanates of aliphatic isocyanates
It is at least one；The hydrophilic modifier is non-ionic hydrophilic modifying agent or ionic hydrophilic modifier.
5. quick-drying water dispersed isocyanate curing agent composition according to claim 4, it is characterised in that: institute
The non-ionic hydrophilic modifying agent stated includes at least one in polyalkylene glycol monoalkyl ether and polyethylene glycol propylene-glycol monoalky lether
Kind；Molecular weight is 200-2000；Shown in its structural formula such as following formula (one):
Wherein, R1For the alkyl of the linear chain or branched chain within C10.
6. quick-drying water dispersed isocyanate curing agent composition according to claim 4, it is characterised in that: institute
The ionic hydrophilic modifier stated is the salt obtained by the sulfonic acid containing amino or hydroxyl with reactive tertiary amine.
7. quick-drying water dispersed isocyanate curing agent composition according to claim 6, it is characterised in that: institute
Shown in the molecular formula such as following formula (two) for stating the sulfonic acid containing amino or hydroxyl:
HO-R2-SO3H or R4-HN-R2-SO3H
(2)
Wherein, R2For the substituted or unsubstituted alkyl of divalent, R4For H or substituted or unsubstituted straight chain, branch or the ring of monovalence
The alkyl of shape；
The tertiary amine is the trialkylamine without hydroxyl or amino group.
8. quick-drying water dispersed isocyanate curing agent composition according to claim 1, it is characterised in that: institute
State non-hydrophilic modification aromatic polyisocyanate part include 50-100 mass parts the structure containing aromatic isocyanate it is more
The solvent of isocyanates and 0-50 mass parts.
9. quick-drying water dispersed isocyanate curing agent composition according to claim 8, it is characterised in that: institute
State the hydrophilic-structure that polyethers, carboxylic acid, sulfonic acid are free of in the structure of the polyisocyanates of the structure containing aromatic isocyanate；Including virtue
In the polyisocyanates that fragrant race's polyisocyanates or aromatic isocyanate are obtained with aliphatic isocyanates mixing copolyreaction
At least one.
10. a kind of system of the described in any item quick-drying water dispersed isocyanate curing agent compositions of claim 1-9
Preparation Method, feature are passing through the aliphatic polyisocyante part of the hydrophilic modifying including 50-95 mass parts, 5-50 mass
The aromatic polyisocyanate part of the non-hydrophilic modification of part is uniformly mixed and obtains.
Priority Applications (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111019078A (en) * | 2019-12-31 | 2020-04-17 | 北京华腾新材料股份有限公司 | Waterborne polyurethane curing agent and preparation method and application thereof |
| CN111393613A (en) * | 2020-04-29 | 2020-07-10 | 广东巴德富新材料有限公司 | Easily-dispersible self-extinction waterborne polyurethane curing agent and preparation method thereof |
| CN111393612A (en) * | 2020-03-20 | 2020-07-10 | 嘉宝莉化工集团股份有限公司 | Sulfonate type waterborne polyurethane curing agent and preparation method and application thereof |
| CN112680087A (en) * | 2020-12-24 | 2021-04-20 | 华南理工大学 | Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof |
| WO2022022529A1 (en) * | 2020-07-31 | 2022-02-03 | Guangdong Huarun Paints Co., Ltd. | Two-component polyurethane coating composition, coating formed from the two-component polyurethane coating composition and coated article |
| CN114133526A (en) * | 2021-12-30 | 2022-03-04 | 佛山市华联有机硅有限公司 | Hydrophilic polyurethane polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111019078A (en) * | 2019-12-31 | 2020-04-17 | 北京华腾新材料股份有限公司 | Waterborne polyurethane curing agent and preparation method and application thereof |
| CN111393612A (en) * | 2020-03-20 | 2020-07-10 | 嘉宝莉化工集团股份有限公司 | Sulfonate type waterborne polyurethane curing agent and preparation method and application thereof |
| CN111393612B (en) * | 2020-03-20 | 2021-11-12 | 嘉宝莉化工集团股份有限公司 | Sulfonate type waterborne polyurethane curing agent and preparation method and application thereof |
| CN111393613A (en) * | 2020-04-29 | 2020-07-10 | 广东巴德富新材料有限公司 | Easily-dispersible self-extinction waterborne polyurethane curing agent and preparation method thereof |
| WO2022022529A1 (en) * | 2020-07-31 | 2022-02-03 | Guangdong Huarun Paints Co., Ltd. | Two-component polyurethane coating composition, coating formed from the two-component polyurethane coating composition and coated article |
| CN112680087A (en) * | 2020-12-24 | 2021-04-20 | 华南理工大学 | Long-activation-period water-based bi-component polyurethane curing agent and preparation method and application thereof |
| CN114133526A (en) * | 2021-12-30 | 2022-03-04 | 佛山市华联有机硅有限公司 | Hydrophilic polyurethane polymer and preparation method thereof |
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Application publication date: 20191018 |