CN109517139A - A kind of Water Dispersible Polyisocyanates composition and preparation method thereof - Google Patents
A kind of Water Dispersible Polyisocyanates composition and preparation method thereof Download PDFInfo
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- CN109517139A CN109517139A CN201811330763.7A CN201811330763A CN109517139A CN 109517139 A CN109517139 A CN 109517139A CN 201811330763 A CN201811330763 A CN 201811330763A CN 109517139 A CN109517139 A CN 109517139A
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- polyisocyanates
- water dispersible
- curing agent
- composition
- polyisocyanate
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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
-
- 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
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
Abstract
The present invention relates to bi-component waterborne resin art, it is related to a kind of Water Dispersible Polyisocyanates composition and preparation method thereof.The composition is according to hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate, mass ratio 10:1~1:3 ratio configuration, and NCO content is the 15~25% of the Water Dispersible Polyisocyanates composition gross mass, and contains fluorochemical polyether segment and amphoteric ion segment；Its preparation step is S1, synthesis hydrophilic modified polyisocyanate curing agent；S2, under nitrogen protection, aromatic polyisocyanate is added in hydrophilically modified polyisocyanates curing agent, 5-40min is stirred, obtains Water Dispersible Polyisocyanates composition.The present invention solves that Water Dispersible Polyisocyanates working life in the prior art is short and the defect of high production cost, obtains a kind of low cost and high performance Water Dispersible Polyisocyanates composition.
Description
Technical field
The present invention relates to bi-component waterborne resin technology fields, more specifically to a kind of water dispersible polyisocyanic acid
Ester composition and preparation method thereof.
Background technique
Cost is relatively low for aromatic polyisocyanate, while also preferable with the performance of cured product after hydroxy component cooperation.
Johnson et al. United States Patent (USP) US3996154 propose using the reaction product of methoxypolyethylene glycol and MDI, TDI, PAPI as
Surfactant, then mixed with MDI, TDI, PAPI, it is prepared for aqueous aromatic polyisocyanates.However aromatic series polyisocyanic acid
The reactivity of ester is very high, quickly with the reaction speed of water, so that its working life in water is very short.In United States Patent (USP)
In US4663377, Rudolf et al. utilizes the MDI of mass fraction 60% and the PAPI mixture and simple function of mass fraction 40%
Polyoxyethylene alcohol reaction is spent, is prepared for Water Dispersible Polyisocyanates, working life is still shorter.In aromatic polyisocyanate by
In the presence of phenyl ring, so that inductive effect occurs between-NCO group, the reactivity of isocyanates is greatly increased, anti-with water
It answers rate to be much higher than aliphatic polyisocyante, after being configured to coating, can react quickly with water and generate urea, so that applying
The crosslink density of material rises rapidly, and working life shortens.So although the aromatic polyisocyanate of hydrophilic modifying have significantly at
The advantage of this and aspect of performance can not also use at present as dual-component aqueous polyurethane curing agent.
Currently, being commercially available widely applied Water Dispersible Polyisocyanates crosslinking agent is by nonionic or anion
Modified aliphatic or alicyclic polyisocyantates composition.United States Patent (USP) US5194487 and US6426414 report use
Polyethers carries out hydrophilic modifying to aliphatic polyisocyante, so that should actually becoming for waterborne two-component polyurethane coating can
Energy.But polyether-modified polyisocyanate curing agent emulsibility in the aqueous polyalcohol emulsion of hydroxyl is not ideal enough, needs
It can just be uniformly dispersed by the machinery of strength.United States Patent (USP) US5583176 and US6767958B2 use the sulfonic acid containing active hydrogen
Salt compound carries out hydrophilic modifying to polyisocyanates, and obtained polyisocyanate curing agent shows good emulsibility.This
Kind has obtained more being widely applied in practical applications by sulfonic acid anion modified polyisocyanate curing agent.However, through
The hydrophily of the polyisocyanates of high emulsibility after crossing hydrophilic modifying is too strong, after it is mixed with hydroxyl latex emulsion, isocyanates
(- NCO) group is easy to react with water, causes the working life of polyisocyanates being dispersed in water very short.
The dual-component aqueous polyurethane prepared using existing anion or nonionic modified polyisocyanate curing agent
The working life of system is still shorter.The it is proposeds such as Chinese patent CN1085682C Zhong Du Bian Shenyi youth, which use, contains polyethylene glycol chain link
Polyethers to polyisocyanates carry out hydrophilic modifying, then compound a certain amount of ionic surfactant again, obtained combination
Object has high emulsibility and long working life.Ionic surfactant mentioned by but is not sent out with polyisocyanates
Raw bonding, causes adverse effect to final dual-component aqueous polyurethane Solidified enzyme as plasticizer.In Chinese patent
The it is proposeds such as city open country filial piety happiness use polyethers with hydroxyl and that ethylene oxide chain link occupies the majority, have hydroxyl in CN101443378B
And the alkali metal salt of polyethers and the sulfonic acid with hydroxyl that propylene oxide chain link occupies the majority carboxylate constitute it is mixed and modified
Agent is modified aliphatic polyisocyante, to improve the working life of polyisocyanate curing agent.In this polyisocyanates
In composition, using the polyethers of hydroxyl end of the above alcohol of 8 carbon as initiator and based on propylene oxide due to hydrophobic effect,
Can play a protective role to isocyanate group, and sulfonate modified dose and polyether-modified dose based on ethylene oxide have it is hydrophilic
Property, polyisocyanates emulsibility can be assigned.But since the amount of hydrophilic modifier is significantly smaller than the amount of polyisocyanates, so that
Hydrophobic grouping and hydrophilic radical are difficult to be bonded on identical polyisocyanate molecule.When this polyisocyantates composition is dispersed in
When in water, the polyisocyanate molecule for being bonded hydrophilic modifying group is in the outer layer of emulsion droplets, and has been bonded hydrophobically modified base
The polyisocyanate molecule of group tends to the internal layer in emulsion droplets, and hydrophobic long-chain is unable to effective protection and is in emulsion droplets outer layer
Polyisocyanate molecule-NCO group, and to extend polyisocyanates working life effect it is limited.Moreover, being dredged introducing
- NCO group is also consumed while water modified group, reduces the performance of curing agent.So the above-mentioned revealed method of patent
The working life of dual-component aqueous polyurethane curing agent cannot be effectively improved and reduce curing agent performance.Chinese patent
The polyether-modified polyisocyanate curing agent of the amphoteric ion used in CN103483574.A can delay water and-NCO to a certain extent
The reaction of group, but the hydrophobicity of polypropylene glycol is lower, and the masking protecting effect of p- NCO group is limited.
No matter currently, nonionic modified or anion-modified, base-material used by dual-component aqueous polyurethane curing agent
It is all aliphatic or alicyclic polyisocyanates, this causes product cost very high, to make to dual-component aqueous polyurethane
Larger obstacle is caused with popularization.In addition, this aliphatic Water Dispersible Polyisocyanates make due to the introducing of hydroaropic substance
The water resistance of its cured product is not still high.Moreover, because its aliphatic design feature makes the mechanical property of its cured product
It can be ideal not enough.And in order to improve the water resistance of cured product and mechanical property, need to improve the crosslink density of cured product,
The dosage for increasing polyisocyanates, to more improve cost.
Summary of the invention
In view of this, the present invention provides a kind of Water Dispersible Polyisocyanates composition and preparation method thereof, to solve
Water Dispersible Polyisocyanates working life is short in the prior art and the defect of high production cost.
A kind of Water Dispersible Polyisocyanates composition includes that hydrophilically modified polyisocyanates curing agent and aromatic series are more
Isocyanates；Wherein, the mass ratio of hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate is 10:1~1:3,
And NCO content is the 15~25% of the Water Dispersible Polyisocyanates composition gross mass, and the Water Dispersible Polyisocyanates
Composition contains fluorochemical polyether segment and amphoteric ion segment.
As a preferred solution of the present invention, the aromatic polyisocyanate is aromatic diisocyanate and fragrant two isocyanides
The tripolymer or polymer derivative of acid esters, i.e., the described aromatic polyisocyanate are the trimerization syntaxy of aromatic diisocyanate
Object or the aromatic polyisocyanate are the polymer derivative or the aromatic series polyisocyanic acid of aromatic diisocyanate
Ester is that aromatic diisocyanate or the aromatic polyisocyanate are the more of aromatic diisocyanate and aromatic diisocyanate
Mer derivatives or the aromatic polyisocyanate are the trimerization syntaxy of aromatic diisocyanate and aromatic diisocyanate
Object or the aromatic polyisocyanate are the polymer or the fragrance of aromatic diisocyanate and aromatic diisocyanate
Race's polyisocyanates is the tripolymer of aromatic diisocyanate and aromatic diisocyanate.
As a preferred solution of the present invention, the aromatic polyisocyanate is toluene di-isocyanate(TDI), diphenyl methane
Diisocyanate, benzene dimethylene diisocyanate, naphthalene diisocyanate, tetramethylxylylene diisocyanate and poly-
Close one of methyl diphenylene diisocyanate or a variety of mixtures.
As a preferred solution of the present invention, the hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate
Mass ratio is 5:1~1:1, and NCO content is the 17~23% of the Water Dispersible Polyisocyanates composition gross mass.
As a preferred solution of the present invention, the hydrophilically modified polyisocyanates curing agent is by aliphatic or alicyclic polyisocyanate
Cyanate reacts synthesis with fluorochemical polyether hydrophilic modifier, and the quality of the fluorochemical polyether hydrophilic modifier accounts for the hydrophilic modifying
The 10.0~50.0% of polyisocyanate curing agent gross mass, the molecular structural formula of the fluorochemical polyether hydrophilic modifier such as formula A institute
Show
Wherein, RfFor containing fluoroalkyl；R is alkyl；X is the integer of 1-20；Y is the integer of 1-20.
As a preferred solution of the present invention, RfSpecially trifluoromethyl-CF3, pentafluoroethyl group-CH2CF3, four fluoropropyls-
CH2CF2CF2H, perfluoro butyl-(CF2)3CF3, perfluoro hexyl-(CF2)5CF3, perfluoro capryl-(CF2)7CF3Or perfluoro hexyl second
Base-CH2CH2(CF2)5CF3；R is specially ethyl-CH2CH3, propyl-CH2CH2CH3Or butyl-CH2CH2CH2CH3；X is 1-10's
Integer；Y is the integer of 1-10.
As a preferred solution of the present invention, the sulfonyl alkyl betaine group in the Water Dispersible Polyisocyanates composition
The 0.4~9.1% of gross mass is accounted for, and the mass ratio of the fluorochemical polyether hydrophilic modifier accounts for the 2.5~45.5% of gross mass.
As a preferred solution of the present invention, the sulfonyl alkyl betaine group in the Water Dispersible Polyisocyanates composition
The 1.4~6.6% of gross mass are accounted for, and the mass ratio of the fluorochemical polyether hydrophilic modifier accounts for the 10.0~33.3% of gross mass.
A kind of preparation method of Water Dispersible Polyisocyanates composition, is used to prepare any right in claim 1-8
It is required that the Water Dispersible Polyisocyanates composition, is prepared:
S1, synthesis hydrophilic modified polyisocyanate curing agent: fluorochemical polyether hydrophilic modifier is first synthesized；Then it is protected in nitrogen
Polyisocyanates is heated to 70-100 DEG C under shield；Then fluorochemical polyether hydrophilic modifier is added into reactor, in catalyst
It is reacted in the presence of dibutyl tin dilaurate, wherein the quality of fluorochemical polyether hydrophilic modifier is polyisocyanic acid
The 5%-30% of the quality of ester, reaction temperature are 80-85 DEG C, reaction time 2.5-3-4h；Then chlorobenzoyl chloride is added to terminate
Reaction, the quality of chlorobenzoyl chloride are the 0.01~0.1% of reactant gross mass；Stop reaction and obtains hydrophilically modified polyisocyanates
Curing agent；S2, under nitrogen protection, aromatic polyisocyanate is added in hydrophilically modified polyisocyanates curing agent, is stirred
Mixing 5-40min is mixed, Water Dispersible Polyisocyanates composition is obtained, wherein hydrophilically modified polyisocyanates curing agent and virtue
The mass ratio of fragrant race's polyisocyanates is 10:1~1:3.
As a preferred solution of the present invention, hydrophilically modified polyisocyanates curing agent and aromatic series polyisocyanic acid in step S2
The mass ratio of ester is 5:1~1:1, and the dynamic viscosity of obtained Water Dispersible Polyisocyanates composition is 4000mPa.s
Hereinafter, NCO content is the 15~25% of gross mass.
It can be seen from the above technical scheme that the invention has the benefit that the present invention utilizes containing in the composition
The hydrophobicity of perfluoroalkyl polyether segment, amphoteric ion and polyisocyanates are spaced apart, the fluorochemical polyether chain with strong hydrophobic effect
Section can effectively cover and protect mutually close on therewith-NCO group, the probability that reduction-NCO group is contacted and reacted with water,
To extend the working life of Water Dispersible Polyisocyanates, reduces cured product and discharge CO2The chance of gas improves bi-component water
Property urethane cures product performance, assign the good emulsibility of polyisocyantates composition, and solidify polyisocyanates
Agent and the water-base resin of the various ionic types including anion, cation and nonionic form curing system, reduce pH
It is worth influence to curing agent emulsion stability, still keeps fairly good cream under the conditions of existing for certain density acid, alkali, the salt
Liquid stability overcomes the short defect of Water Dispersible Polyisocyanates working life in the prior art；Utilize two in the composition
Property ion fragment in hydrophily make the composition that there is good water dispersible property, and absorb amphoteric surfactant
Advantage is used for modified polyisocyanate, makes the composition have both the electricity of stability in hard water, resisting high-concentration using amphoteric ion segment
Matter and good emulsibility and dispersibility are solved, anion-modified polyisocyanate curing agent restricted application is overcome
Defect；In addition, the present invention increases the composition using aromatic series-NCO group of high reaction activity in aromatic polyisocyanate
Stability in hard water, resisting high-concentration electrolyte and good emulsibility and dispersibility, and due to aromatic polyisocyanate
Aromatic series-NCO group of middle high reaction activity tends to the inside in emulsion droplets and is covered and protect by fluorochemical polyether segment, subtracts
The probability that few-NCO group is contacted and reacted with water further overcomes to extend the working life of Water Dispersible Polyisocyanates
Water Dispersible Polyisocyanates working life short defect in the prior art, and the preparation cost of aromatic polyisocyanate is lower than
The preparation cost of hydrophilically modified polyisocyanates curing agent, aromatic polyisocyanate is formed to composition in proportion effectively to drop
The production cost of low Water Dispersible Polyisocyanates, so that it is short to solve Water Dispersible Polyisocyanates working life in the prior art
And the defect of high production cost, obtain a kind of low cost and high performance Water Dispersible Polyisocyanates composition.
Detailed description of the invention
The nuclear magnetic resonance spectroscopy that Fig. 1 is polyethers A prepared by the embodiment of the present invention 1 analyzes map.
Fig. 2 is the Fourier transform infrared light map of polyethers A prepared by the embodiment of the present invention 1.
Fig. 3 is the electrospray ionization mass spectrometry map of polyethers A prepared by the embodiment of the present invention 1.
The Enantiomeric excess that Fig. 4 is polyethers B prepared by the embodiment of the present invention 1 analyzes map.
The Enantiomeric excess that Fig. 5 is polyethers C prepared by the embodiment of the present invention 2 analyzes map.
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing described in technical description to be briefly described, it is therefore apparent that the attached drawing in description below is only of the invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other attached drawings.
Specific embodiment
Following example is for present invention be described in more detail, but embodiment does not do any type of limit to the present invention
Fixed, except illustrating, reagent that the present invention uses, method and apparatus are the conventional reagent of the art, method and apparatus,
But the invention is not limited in any way.
A kind of Water Dispersible Polyisocyanates composition includes that hydrophilically modified polyisocyanates curing agent and aromatic series are more
Isocyanates；Wherein, the mass ratio of hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate is 10:1~1:3,
And NCO content is the 15~25% of the Water Dispersible Polyisocyanates composition gross mass, and the Water Dispersible Polyisocyanates
Composition contains fluorochemical polyether segment and amphoteric ion segment.The aromatic polyisocyanate is aromatic diisocyanate and virtue
The tripolymer or polymer derivative of fragrant diisocyanate.The aromatic polyisocyanate is toluene di-isocyanate(TDI), hexichol
Dicyclohexylmethane diisocyanate, benzene dimethylene diisocyanate, naphthalene diisocyanate, tetramethylxylylene diisocyanate
And one of polymeric diphenylmethane diisocyanate or a variety of mixtures.More specifically, the aromatic series polyisocyanic acid
Ester is hexamethylene diisocyanate.The mass ratio of the hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate
For 5:1~1:1, NCO content is the 17~23% of the Water Dispersible Polyisocyanates composition gross mass.The hydrophilic modifying is more
Isocyanate curing agent, which is reacted by aliphatic or alicyclic polyisocyanates with fluorochemical polyether hydrophilic modifier, to be synthesized, and described is contained
The quality of perfluoroalkyl polyether hydrophilic modifier accounts for the 10.0~50.0% of the hydrophilically modified polyisocyanates curing agent gross mass, this is fluorine-containing
The molecular structural formula of Polyether hydrophilic agent is as shown in formula A
Wherein, RfFor containing fluoroalkyl；R is alkyl；X is the integer of 1-20；Y is the integer of 1-20.RfSpecially fluoroform
Base-CF3, pentafluoroethyl group-CH2CF3, four fluoropropyl-CH2CF2CF2H, perfluoro butyl-(CF2)3CF3, perfluoro hexyl-(CF2)5CF3、
Perfluoro capryl-(CF2)7CF3Or perfluoro hexyl ethyl-CH2CH2(CF2)5CF3；R is specially ethyl-CH2CH3, propyl-
CH2CH2CH3Or butyl-CH2CH2CH2CH3；X is the integer of 1-10；Y is the integer of 1-10.The Water Dispersible Polyisocyanates group
The sulfonyl alkyl betaine group closed in object accounts for the 0.4~9.1% of gross mass；And the quality of the fluorochemical polyether hydrophilic modifier
Than account for gross mass 2.5~45.5%.Sulfonyl alkyl betaine group Zhan in the Water Dispersible Polyisocyanates composition is total
The 1.4~6.6% of quality, and the mass ratio of the fluorochemical polyether hydrophilic modifier accounts for the 10.0~33.3% of gross mass.Using
The dynamic viscosity of this mixing polyisocyanates being modified that rotary viscometer determines is 4000mPa.s hereinafter, preferably
2000mPa.s following.
A kind of preparation method of Water Dispersible Polyisocyanates composition, is used to prepare any right in claim 1-8
It is required that the Water Dispersible Polyisocyanates composition, is prepared:
S1, synthesis hydrophilic modified polyisocyanate curing agent: fluorochemical polyether hydrophilic modifier is first synthesized；Then it is protected in nitrogen
Polyisocyanates is heated to 70-100 DEG C under shield；Then fluorochemical polyether hydrophilic modifier is added into reactor, in catalyst
It is reacted in the presence of dibutyl tin dilaurate, wherein the quality of fluorochemical polyether hydrophilic modifier is polyisocyanic acid
The 5%-30% of the quality of ester, reaction temperature are 80-85 DEG C, reaction time 2.5-3-4h；Then chlorobenzoyl chloride is added to terminate
Reaction, the quality of chlorobenzoyl chloride are the 0.01~0.1% of reactant gross mass；Stop reaction and obtains hydrophilically modified polyisocyanates
Curing agent.
In step sl, the synthesis process of fluorochemical polyether hydrophilic modifier is as follows:
S11, synthesis tertiary amine groups polyether monol: with propylene oxide be monomer and dialkylamine is initiator, by yin from
Sub- ring-opening polymerisation synthesizes the tertiary amine groups polyether monol that there is hydroxyl in one end and the other end has tertiary amine groups；Wherein, propylene oxide is single
The molar ratio of body and dialkylamine is 2:1~30:1, and preferably 2:1~20:1 is more highly preferred to 5:1~10:1；Step S11's is specific
Process are as follows: S111, using dialkylamine as initiator and the propylene oxide of metering ring-opening polymerization in a high pressure reaction kettle；
Temperature is reduced when autoclave aging to normal pressure to obtain tertiary amine groups polyether monol crude product.Wherein, autoclave is adopted
With nitrogen protection, propylene oxide is that the molar ratio of monomer and dialkylamine is 2:1~30:1, and preferably 2:1~20:1 is more highly preferred to
5:1~10:1；Select potassium hydroxide KOH as catalyst, the quality of catalyst is the 0.05%-2% of monomer mass, preferably
0.1%-1%, more preferably, 0.2%-0.5%.Initial reaction temperature is controlled at 100-150 DEG C；S112, gather in tertiary amine groups
The distilled water of the quality such as addition and stirring in ether monohydric alcohol crude product.Then it is added with the equimolar 0.1mol/L's of catalyst KOH
Dilute hydrochloric acid neutralizes.Finally, and removing moisture removal through vacuum distillation；S113, n-hexane is added as water entrainer, the quality of n-hexane
For 0.5-2 times of polyether quality, preferably 1-1.5 times；By distilling the water in further removal tertiary amine groups polyether monol crude product
Point；S14, n-hexane, the tertiary amine groups polyether monol refined are removed finally by vacuum distillation；
S12, synthesis amphoteric ion polyether monol: it reacts to obtain with tertiary amine groups polyether monol using propane sulfonic acid lactones
Amphoteric ion polyether monol with amphoteric ion group.Propane sulfonic acid lactones and the molar ratio of tertiary amine groups polyether monol are
1:1~1.5:1, preferably 1:1~1.1:1, are more highly preferred to 1:1~1.05:1；Step S2's specifically: use 1,3- propane sulfonic acid
Lactone carries out sulfopropyl with tertiary amine groups polyether monol and reacts the amphoteric ion polyethers unitary that preparation has amphoteric ion group
Alcohol；The molar ratio of propane sulfonic acid lactones and tertiary amine groups polyether monol is 1:1~1.5:1, and preferably 1:1~1.1:1 is more highly preferred to
1:1~1.05:1；
S13, synthesis fluorochemical polyether hydrophilic modifier: using amphoteric ion polyether monol as initiator, with ring containing fluoroalkyl
Ethylene Oxide is monomer, and the end of amphoteric ion polyether monol is grafted to by cation ring-opening polymerization fluorochemical polyether segment, is obtained
To the fluorochemical polyether hydrophilic modifier with amphoteric ion group.Amphoteric ion polyether monol and fluorine-containing alkyl epoxy propane
Mass ratio is 1:0.5~1:8, and preferably 1:1~1:5 is more highly preferred to 1:1~1:3；The detailed process of step S13 includes:
S131, methylene chloride, the amphoteric ion polyether monol of amphoteric ion group and catalyst boron trifluoride ether are complexed
Object and tetrabutylammonium bromide are added to equipped in flask and stirring；The quality of methylene chloride is amphoteric ion polyether monol
0.5-5 times of quality, preferably 1-3 times, more preferably 1.5-2 times；The quality of catalyst boron trifluoride etherate is two
0.1%-5%, the preferably 0.5%-5% of property ion polyether monol, more preferably 0.5%-3%；Catalyst tetrabutyl bromine
The quality for changing ammonium is the 0.1%-5%, preferably 1%-5%, more preferably 1%-3% of amphoteric ion polyether monol.S132,
Pot temperature is down to 0 DEG C with cryogenic thermostat circulating slot, fluorine-containing alkyl epoxy propane is added dropwise after stirring 20-30min.Both sexes from
The mass ratio of sub- polyether monol and fluorine-containing alkyl epoxy propane is 1:0.5~1:8, preferably 1:1~1:5, be more highly preferred to 1:1~
1:3；It maintains temperature of reaction system at -1 DEG C to 1 DEG C, time for adding 2-3h, after being added dropwise, keeps the temperature-resistant continuation
React 3-4h；S133,30ml water is added under stirring to terminate polymerization reaction；S134, it is removed by distillation under vacuum
Solvent and moisture obtain fluorine-containing amphoteric ion polyether monol crude product.Step S13 further includes having: S135, fluorine-containing two will obtained
Property ion polyether monol crude product isopropanol solvent dilution is added, the quality of isopropanol solvent is fluorine-containing amphoteric ion polyethers unitary
0.5-5 times of alcohol crude product, preferred mass 1-5, more preferably 1-2 times；S136, magnesium silicate adsorbent is then added, and passes through
Filter press removes the salt and adsorbent precipitated in fluorine-containing amphoteric ion polyether monol crude product；The quality of magnesium silicate adsorbent be containing
0.1-1 times of polyether monol of fluorine amphoteric ion, preferably 0.1-0.5 times, more preferably 0.1-0.3 times；S137, it further uses
Strong-acid cation-exchange resin processing, until the alkali metal content in obtained fluorine-containing amphoteric ion polyether monol crude product drops to
5ppm or less；S138, exquisite fluorine-containing amphoteric ion polyether monol is obtained after removing isopropanol solvent with distillation under vacuum again,
Obtain fluorochemical polyether hydrophilic modifier.Join simultaneously in the fluorochemical polyether hydrophilic modifier by the polyisocyanates of hydrophilic modifying
Hydrophobic fluorochemical polyether segment and hydrophilic amphoteric ion segment are connect.Polyisocyanates in the fluorochemical polyether hydrophilic modifier
It is based on aliphatic or alicyclic polyisocyanates, these polyisocyanates can be including hexamethylene diisocyanate
(HDI), isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methyl hydride diisocyanates (H12MDI), hexamethylene two are different
All aliphatic including cyanate (CHDI) and 1,3- bis- (isocyanatomethyl) hexamethylene (H6XDI) are alicyclic two different
The trimer derivatives of cyanate, the preferably tripolymer of HDI.
S2, under nitrogen protection, aromatic polyisocyanate is added in hydrophilically modified polyisocyanates curing agent, is stirred
Mixing 5-40min is mixed, Water Dispersible Polyisocyanates composition is obtained, wherein hydrophilically modified polyisocyanates curing agent and virtue
The mass ratio of fragrant race's polyisocyanates is 10:1~1:3.Hydrophilically modified polyisocyanates curing agent and aromatic series are more in step S2
The mass ratio of isocyanates is 5:1~1:1, and the dynamic viscosity of obtained Water Dispersible Polyisocyanates composition is
4000mPa.s is hereinafter, NCO content is the 15~25% of gross mass.
Below with reference to embodiment, the present invention will be further described:
The synthesis of fluorochemical polyether hydrophilic modifier:
Embodiment 1
As shown in Figs 1-4, using diethylamide as initiator, using KOH as catalyst propylene oxide ring-opening polymerisation.
Synthesis is carried out in autoclave of the dry 1L of cleaning with stirring.2.8g KOH is first placed in autoclave
Then the operation of vacuum nitrogen gas autoclave is repeated in catalyst.Then it is added at room temperature into kettle
111.0g (~1.52eq) chromatographically pure grade (purity >=99.5%) diethylamide synthesizes single functionality polyethers as initiator.In room
Under temperature, 3.6 bars of nitrogen are imported.Then it is pressed into 40g propylene oxide, reaction kettle is gradually warmed up to 125 DEG C of progress induced reactions.When
Reaction pressure bust when temperature is increased beyond 5 DEG C, shows that induced reaction terminates.In subsequent 30 minutes 3 hours time to
426g propylene oxide is gradually added in autoclave.Mixture continues to be stirred to react 50 minutes.Under 105 DEG C and 10 millibars
Exhaust, is collected by filtration tertiary amine groups polyether monol.Reaction equation is such as shown in (1):
Above-mentioned prepared tertiary amine groups polyethers sample 571g (~1.52eq) is transferred in 1000ml four-hole boiling flask, in temperature
The small molecule of removed under reduced pressure remnants at 80 DEG C of degree.Then the HCl solution 100ml catalyst neutralisation that concentration is 0.5mol/L is added
KOH point falls water layer after standing.Under nitrogen protection, by the mixture vacuum distillation removing moisture after reaction, it is poly- that tertiary amine groups are obtained
Ether monohydric alcohol.
Above-mentioned made tertiary amine groups polyethers sample 131.6g (~0.35eq) is taken to be placed in 500ml three-necked flask, Xiang Fanying
1,3- propane sultone 42.8g (~0.35eq) and acetone 100ml is added in bottle, heating reflux reaction 24 is small under stirring
When, it reacts as shown in formula (2).It reduces temperature and stops reaction.Acetone solvent is removed by vacuum distillation, obtains amphoteric ion polyethers
Monohydric alcohol sample is denoted as polyethers A.
Physical property measurement is carried out to the polyethers A of acquisition, measuring its hydroxyl value is 112.36mg KOH/g, viscosity 450mPa.s.
To polyethers A carry out hydrogen nuclear magnetic resonance spectrum analysis (1H-NMR), as shown in Figure 1:
The corresponding chemistry of each absorption peak of a-f in Fig. 1 is judged according to the chemical shift of the intensity of nuclear-magnetism absorption peak and absorption peak
Structure are as follows: a: δ=3.25-3.79ppm (m ,-OCH2CH(CH3)-and-CH2CH2 CH2 -SO3 -)；B: δ=3.12-3.19ppm
(t ,-CH2 CH2CH2-SO3 -)；C: δ=2.85-3.08ppm (m ,-OCH2 CH(CH3)-N+(CH2CH3)2And-N+(CH2 CH3)2-)；
D: δ=2.65 (s ,-OH)；E: δ=2.10-2.21ppm (m ,-CH2 CH2 CH2-SO3 -)；F: δ=1.55-1.61ppm (m ,-N+
(CH2 CH3 )2-)；G: δ=0.96-1.20ppm (m ,-OCH2CH(CH3 )-and-OCH2CH(CH3 )-N+(CH2CH3)2-).Nuclear-magnetism hydrogen
Spectrum is further demonstrated there are a large amount of polyethers chain link in product, and absorption peak b and e show that there are the third sulfo groups in product.
It is characterized using product A of the Fourier transform infrared spectroscopy (FT-IR) to synthesis, sees Fig. 2.Wherein, it is located at
3455.5cm-1Strong absworption peak be hydroxyl O-H stretching vibration peak；2989cm-1And 2882cm-1The absorption peak at place is-CH3No
Symmetrical stretching vibration and-CH2Symmetrical stretching vibration absorption peak；1476cm-1The peak at place is-CH2Scissoring vibration or-CH3Antisymmetry
Vibration absorption peak；1356cm-1Place's absorption peak is-CH2Deformation vibration peak；1230cm-1Place peak is-SO3Symmetrical stretching vibration
Absorption peak；1112cm-1Place is the asymmetric stretching vibration absorption peak of ehter bond C-O-C；1038cm-1Peak be C-N stretching vibration inhale
Receive peak, 620.3cm-1Peak S-O key stretching vibration absworption peak.This illustrates that there are hydroxyl, ehter bond and sulfonic groups in product, meet poly-
The structure feature of ether A.
It is characterized using product A of the electrospray ionization mass spectrometry (ESI-MS) to synthesis, sees Fig. 3.Each two neighboring molecule
Quasi-molecular ions interstitial nucleus ratio (m/z) difference about 58, the exactly equal to molecular weight of propylene oxide, illustrate that molecule is by Polymerization of Propylene Oxide
The mixture of obtained different molecular weight.The m/z numerical value of each molecular ion peak is also close to the molecular structure for meeting polyethers A.In addition,
Highest peak abundance (Relative Abundance) of molecular ion peak appears in the section m/z=426~542, and by reality
The hydroxyl value of measurement is 112.36mg KOH/g, and containing a hydroxyl according to each pfpe molecule can be poly- with calculated amphoteric ion
The theoretical average molecular weight of ether is 498.4g/mol, is in this section.Comprehensive analysis mass spectrum, it is infrared and nuclear-magnetism the result shows that,
The structure of product A is to meet amphoteric ion polyethers shown in reaction equation (2).
By 60g dry dichloromethane solvent, 40g polyethers A (as initiator), 0.8g tetrabutylammonium bromide, 1.2g tri-
Fluorination borate ether (as catalyst) is added in the three-necked flask equipped with blender and thermometer, starts to stir.Use refrigerator
Temperature of reaction system is down to 0 DEG C or so, starts the 3- (2,2,3,3- tetrafluoro propoxyl group)-that 38g is added dropwise after stirring 20-30min
1,2- propylene oxide, and maintain temperature of reaction system at 0 DEG C or so, time for adding about 2h.After being added dropwise, the temperature is kept not
Become the reaction was continued 3h.Then, 200g water is added and stirs 5min, to destroy catalyst and terminate polymerization reaction.And it will be insoluble
It mutually removes, then is evaporated under reduced pressure in the oil of water, obtain fluorochemical polyether monohydric alcohol, be denoted as polyethers B.It is fluorine-containing poly- by what is obtained
After ether monohydric alcohol carries out vaccum dewatering 1h, it is sealed.Reaction equation is such as shown in (3):
It takes polyethers B that isopropanol 100ml dilution is added, adds a certain amount of 30g magnesium silicate adsorbent and stir evenly, it is then quiet
It sets 2-3 hours.The adsorbent and salt in polyethers are removed by plate and frame type filter-press, then vacuum distillation removal isopropanol.Into one
Step handles polyethers B using strong-acid cation-exchange resin (001 × 7 model), until the potassium ion K in polyethers+With sodium ion Na+
Content is to 5ppm or less.To polyethers B carry out Enantiomeric excess analysis (19F-NMR), as shown in Figure 4.According to nuclear-magnetism absorption peak
The chemical shift of intensity and absorption peak judges the corresponding chemical structure of each absorption peak of a, b in Fig. 4 are as follows: a: δ=- 128,17ppm
(s ,-CF2-)；B: δ=- 128,17ppm (d ,-CF2H).Enantiomeric excess shows that polyethers B is to meet containing in reaction equation (3)
Fluorine amphoteric ion polyethers.The test of physical property is carried out to the polyethers B of acquisition, the property for obtaining polyethers B is as follows:
The hydroxyl value of polyethers B: 58.75mg KOH/g；
The viscosity of polyethers B: 470mPa.s；
K++Na+Content: 5ppm.
Embodiment 2
As shown in figure 5, using polyethers A as raw material, by 85g dry dichloromethane solvent, 40g polyethers A (as starting
Agent), 1.1g tetrabutylammonium bromide, 1.2g boron trifluoride ether (as catalyst) be added to equipped with blender and thermometer three
In mouth flask, start to stir.Temperature of reaction system is down to 0 DEG C or so with refrigerator, after stirring 20-30min starts that 72g is added dropwise
3- (2- perfluoro hexyl ethyoxyl) -1,2- propylene oxide, and maintain temperature of reaction system at 0 DEG C or so, time for adding about 2h.
After being added dropwise, temperature-resistant the reaction was continued the 3h is kept.Then, 200g water is added and stirs 5min, to destroy catalyst
And terminate polymerization reaction.And mutually remove oil not soluble in water, then be evaporated under reduced pressure, fluorochemical polyether monohydric alcohol is obtained,
It is denoted as polyethers C.After obtained fluorochemical polyether monohydric alcohol is carried out vaccum dewatering 1h, it is sealed.Reaction equation is such as shown in (4):
To polyethers C carry out Enantiomeric excess analysis (19F-NMR), as shown in Figure 5.According to the intensity of nuclear-magnetism absorption peak and
The chemical shift of absorption peak judges the corresponding chemical structure of each absorption peak of a-f in Fig. 4 are as follows: a: δ=- 80.85ppm (s ,-
CF2CF2CF2CF2CF2 CF 3)；B: δ=- 114.29ppm (s ,-CF 2CF2CF2CF2CF2CF3)；C: δ=- 121.91ppm (s ,-
CF2 CF 2CF2CF2CF2CF3)；D: δ=- 122.85ppm (s ,-CF2CF2 CF 2CF2CF2CF3)；E: δ=- 123.51ppm (s ,-
CF2CF2CF2 CF 2CF2CF3)；F: δ=- 126.16ppm (s ,-CF2CF2CF2CF2 CF 2CF3).Enantiomeric excess shows polyethers C
It is the fluorine-containing amphoteric ion polyethers met in reaction equation (4).The test that physical property is carried out to the polyethers C of acquisition, obtains its property such as
Under:
The hydroxyl value of polyethers C: 41.23mg KOH/g；
The viscosity of polyethers C: 480mPa.s；
K++Na+Content: 5ppm.
The synthesis of hydrophilically modified polyisocyanates curing agent:
Embodiment 3
Using tripolymer (HDT) product of hexamethylene diisocyanate (HDI) as polyisocyanates matrix, more than this kind
The viscosity of isocyanates is 1400mPa.s, NCO group content 23.1%.By 300g (NCO group content~1.65eq) polyisocyanate
Cyanate is placed in 500ml four-hole boiling flask, and 0.5g dibutyl tin laurate is added as catalyst.Flask be passed through drying nitrogen into
Row protection, is heated to 80 DEG C for reaction, a certain amount of polyethers B (being shown in Table 1) is added dropwise under stirring, is added dropwise in 30min.After
Continuous reaction 2h is added 0.2g chlorobenzoyl chloride, stops reaction, obtain colourless or yellowish when the content of-NCO group reaches 18.6%
The product of color clear viscous.After hydrophilic modifying-theoretical value of NCO group content is by the amount and its hydroxyl using hydrophilic modifying polyethers
Value calculates.By taking embodiment 3 as an example, the hydroxyl value of hydrophilic modifier polyethers B is 58.75mg KOH/g, then its theoretical molecular weight is
953g/mol.Assuming that the total amount of polyisocyanates and polyethers is 100g, then when using 11.36% polyethers B as hydrophilic modifier
The amount of polyisocyanates is 88.64g, and polyethers B is 11.36g.By polyethers consumption-amount of NCO group be (11.36g ×
58.75×10-3)/56.1g/mole × 42.02g=0.5g, then after hydrophilic reaction-NCO group theoretical value be (88.64g ×
0.231-0.5g)/100g=19.97%.
The synthesis of hydrophilically modified polyisocyanates composition:
Embodiment 4
Prepared polyisocyanates 150g is placed in the three-necked flask with stirring in Example 3, is passed through dry
Nitrogen.Tetramethylxylylene diisocyanate (TMXDI) 75g is added under nitrogen protection, is stirred at room temperature
15min obtains a kind of polyisocyantates composition of hydrophilic modifying.
Embodiment 5
Operation same as Example 4 is carried out at identical conditions, and two methylene of durol is added under nitrogen protection
Group diisocyanate (TMXDI) 60g, is stirred 15min at room temperature, obtains a kind of polyisocyanates combination of hydrophilic modifying
Object.
Embodiment 6
Operation same as Example 4 is carried out at identical conditions, and tetramethylxylene is added under nitrogen protection
Diisocyanate (TMXDI) 45g, is stirred 15min at room temperature, obtains a kind of polyisocyantates composition of hydrophilic modifying.
Embodiment 7
Use polyisocyanates same as Example 3 for matrix.By 600g (NCO group content~1.65eq) polyisocyanate cyanogen
Acid esters is placed in 1000ml four-hole boiling flask, and 0.5g dibutyl tin laurate is added as catalyst.Flask be passed through drying nitrogen into
Row protection, is heated to 80 DEG C for reaction, is added dropwise in 168g polyethers C, 30min and is added dropwise under stirring.The reaction was continued 2h,
When the content of-NCO group reaches 17.4%, 0.2g chlorobenzoyl chloride is added, stops reaction, obtains colorless and transparent sticky production
Object.
Embodiment 8
Prepared polyisocyanates 150g is placed in the three-necked flask with stirring in Example 7, is passed through dry
Nitrogen.Polymeric diphenylmethane diisocyanate (PAPI) 75g is added under nitrogen protection, is stirred 15min at room temperature, obtains
To a kind of polyisocyantates composition of hydrophilic modifying.
Embodiment 9
Operation same as Example 4 is carried out at identical conditions, and polymeric diphenylmethane is added under nitrogen protection
Diisocyanate (PAPI) 60g, is stirred 15min at room temperature, obtains a kind of polyisocyantates composition of hydrophilic modifying.
Embodiment 10
Operation same as Example 4 is carried out at identical conditions, and polymeric diphenylmethane two is added under nitrogen protection
Isocyanates (PAPI) 45g, is stirred 15min at room temperature, obtains a kind of polyisocyantates composition of hydrophilic modifying.
Embodiment 11 (comparative example)
Using 3- (cyclohexylamino) -1- propane sulfonic acid (CAPS), N, N- dimethyl cyclohexyl amine and with example 4 above~12
Identical polyisocyanates does the anion-modified polyisocyanate curing agent of Material synthesis.By 180g (~1.10eq) polyisocyanic acid
Ester is placed in 500ml four-hole boiling flask, be added 80ml propylene glycol methyl ether acetate (PMA) be used as solvent, add 5.6g CAPS and
3.2g N, N- dimethyl cyclohexyl amine, using 0.5g dibutyl tin laurate as catalyst.Flask is passed through drying nitrogen and is protected
Shield, is heated to 80 DEG C of reaction 4h for reaction, obtains colourless transparent solution.Vacuum distillation removal solvent obtains colorless and transparent viscous fluid
Body, sample are denoted as Control.
Hydrophilically modified polyisocyanates curing agent performance evaluation: water dispersion test
At room temperature, it takes 10g to pass through the polyisocyantates composition of hydrophilic modifying, distributes it to 50ml deionized water
In, mixture is dispersed into 10min using high speed disperser at 800 rpm, 10min is stood, visually observes the shape of aqueous dispersions
State, dispersity are evaluated according to following standard:
× --- -- has oil droplet and micelle always, does not can be uniformly dispersed；
Δ --- --- is can be uniformly dispersed, but white opacity state is presented；
√ --- --- is evenly dispersed, forms fine and smooth lotion, shows slightly transparent.
The working life that polyisocyanates is dispersed in water is that-the NCO of the polyisocyanates by tracking titration in water contains
Amount is to determine.By timing being distributed in water, polyisocyanates-time for sharply declining of NCO content is defined as its point
Dissipate working life in water.
The preparation of waterborne two-component polyurethane coating (2K-WPU):
Anionic hydroxyl group lotion is used as using the hydroxyl acrylic emulsion Bayhydrol XP 2546 of Bayer company, is taken
120g Bayhydrol XP 2546 respectively can water with the series synthesized in 30g Control and example 4~6 and example 8~10
Dispersible polyisocyanate curing agent mixing composition 2K-WPU coating.Similar, the cation synthesized in example 11 using 160g
Polyaminoester emulsion is respectively at the above-mentioned Water Dispersible Polyisocyanates curing agent mixing composition 2K-WPU coating of 25g.Observation mixing point
Emulsion state evaluates 2K-WPU coating state according to following standard after dissipating:
× --- -- is agglomerated, and stable lotion cannot be formed；
√ --- --- can form stable 2K-WPU lotion.
Test 2K-WPU viscosity of the coating and working life.The working life of 2K-WPU coating is true using the glossiness method of film
Fixed, because 2K-WPU is placed more than after its working life, mechanical performance and coating film gloss can all be varied widely, and will place
The deployed 2K-WPU paint brush of different time is coated in tinplate sheet, measures the angle all coated film sample 60o glossiness, wherein
The sample that glossiness is decreased obviously corresponding standing time is determined as the working life of 2K-WPU.2K-WPU coating is coated in poly-
It forms a film on the mold of tetrafluoroethene, is removed after dry.It takes the film of 5cm × 5cm to weigh up weight and is denoted as m0, be put into distilled water
For 24 hours, weight is weighed after taking-up and be denoted as m0, calculate water absorption rate=(m1-m0)/m0.
As it can be seen from table 1 being showed by modified aliphatic polyisocyante and aromatic polyisocyantates composition
Good water dispersible property out.Moreover, in the polyisocyanates being made of polyethers B modified aliphatic polyisocyanates and TMXDI
The working life that composition is dispersed in water is 3-3.5 hours, and is formed by polyethers C modified aliphatic polyisocyanates and PAPI
Working life for being dispersed in water of polyisocyantates composition be 2.5-3 hours, this may be primarily due to reaction of the PAPI to water
Activity is greater than TMXDI to the reactivity of water, so that its working life reduces.But obtained by embodiment 4-6 and embodiment 8-10
Polyisocyanates working life it is close with using anion-modified fatty polyisocyanates, come from the angle of its processing performance
It sees, these, which contain aromatic hydrophilically modified polyisocyanates, can be used as the use of Water Dispersible Polyisocyanates curing agent.And
Why polyisocyantates composition containing aromatic polyisocyanate, which shows good processing performance, is primarily due to make
The fluorochemical polyether segment of standby hydrophilic modifier provides protection to-NCO group.In addition, aromatic series in mixing polyisocyanates
Polyisocyanates only account for certain ratio, and aliphatic polyisocyante accounts for very big specific gravity, so that mixing polyisocyanates
Working life be improved.
From table 2 it can be seen that embodiment 4-6 and embodiment 8-10 are obtained after forming 2K-WPU with anionic emulsion
The working life of polyisocyanates is close with using anion-modified fatty polyisocyanate sample Control.Meanwhile with use
Anion-modified fatty polyisocyanates is compared, using embodiment 4-6 and the obtained polyisocyanates system of embodiment 8-10
Standby 2K-WPU coating shows higher hardness.This is primarily due to, and has aromatic series in embodiment 4-6 and embodiment 8-10
Polyisocyanates, the mechanical property of cured product is better than the cured product of aliphatic polyisocyanates.In addition, and sample
Product Control is compared, modified polyisocyanate obtained by embodiment 4-6 and embodiment 8-10-NCO group content is higher, make
The crosslink density for obtaining its cured product improves, thus shows higher hardness.Compared with sample Control, by embodiment 4-6
Lower water absorption rate is shown with the 2K-WPU coating of the preparation of modified polyisocyanate obtained by embodiment 8-10.This be mainly because
It is higher for its crosslink density, and fluorine-containing polyether segment is introduced in the component of curing agent, hydrophobic effect is played, thus
Show higher water resistance.
1. hydrophilically modified polyisocyanates curing agent performance of table
* modifying agent quality: refer to that hydrophilic modifier accounts for polyisocyanates and the total mass percent of hydrophilic modifier.
*-NCO (%): refer to after the completion of reaction at room temperature place 3 days after measure-NCO group content.
2. double-component waterborne polyurethane coating 2K-WPU of table
It is disclosed in this invention it is a kind of by modified aliphatic polyisocyante and aromatic polyisocyanate due to special
Formula composition and fluorochemical polyether hydrophilic modifier special molecular structure aromatic polyisocyanate can be used as can
The component of water dispersible polyisocyanate.Make the cost of Water Dispersible Polyisocyanates due to using aromatic polyisocyanate
It reduces, and mechanical property is improved.In addition, due in modifying agent fluorochemical polyether structure exist so that after solidifying film it is resistance to
It is aqueous to be improved.
Obviously, aliphatic polyisocyante conduct is used in Water Dispersible Polyisocyanates composition provided by the present invention
Hydrophilic modifying component, when this Water Dispersible Polyisocyanates composition to be dispersed in water, these have been bonded hydrophilic modifying
The fat race polyisocyanates of agent tends to the outer layer in emulsion droplets, and aromatic polyisocyanates tends in emulsion droplets
Inside.Aromatic series-NCO group of high reaction activity can be protected by the aliphatic polyisocyanates of low reaction activity.Parent
Fluorochemical polyether segment on water modifying agent also provides protective effect to emulsion droplets inside-NCO group.Therefore, in the present invention may be used
Using the constituent as Water Dispersible Polyisocyanates using aromatic polyisocyanate, to reduce water dispersible more
The cost of isocyanates.Since aromatic series polyisocyanate can be used in Water Dispersible Polyisocyanates composition provided by the present invention
Cyanate, therefore the mechanical property of cured product can be improved.As the crosslinking agent of aqueous high molecular, polyisocyanates passes through introducing
Amphoteric ion segment realizes water dispersible property as hydrophilic radical, and water-base resin itself also tends to draw on molecular structure
Enter amphoteric ion segment as hydrophilic radical or using surfactant, this makes using Water Dispersible Polyisocyanates as crosslinking agent
The problem of cured product of the double-component waterborne polyurethane system of composition is also frequently present poor water resistance.The present invention passes through in modification
Hydrophobic fluorochemical polyether segment is introduced in agent, and the water resistance of the cured product of double-component waterborne polyurethane system can be made to obtain
It improves.Entire composition can regard a kind of amphoteric ion segment of zwitterionic surfactant with hydroxyl as, wherein sulphur
Base alkyl betaines base groups are hydrophilic amphoteric ion segment, and fluorochemical polyether is hydrophobic segment.It is modified with this hydrophilic modifier
Polyisocyanate curing agent can be made to obtain good water dispersible property.With it is existing anion-modified water dispersible in the market
Polyisocyanates is compared, and the composition of this fluorine-containing amphoteric ion polyether monol modifying agent not only assigns polyisocyanates combination
The good emulsibility of object, and make polyisocyanate curing agent with including anion, cation and nonionic it is various from
The water-base resin of subtype forms curing system.Influence of the pH value to curing agent emulsion stability can be reduced, in a certain concentration
Acid, alkali, existing for salt under the conditions of still keep fairly good stability of emulsion.This is because amphoteric ion segment is hydrophilic
Group not only has anion part, but also tool cationic portion, in the solution the electrical properties such as display.There are many excellent performances for it: packet
The electrolyte of fabulous stability in hard water and resisting high-concentration is included, can be with various types surfactant compatibility, there are also good creams
The property changed and dispersibility etc..Therefore, the present invention absorbs the advantages of amphoteric surfactant, is used for modified polyisocyanate, overcomes
The shortcomings that anion-modified polyisocyanate curing agent restricted application.And use this fluorine-containing amphoteric ion polyethers unitary
The working life of polyisocyanate curing agent can be improved in the composition of alcohol modifying agent.Using anion-modified dose of polyisocyanates
When composition is dispersed in water, it is in the outermost of emulsion droplets by modified polyisocyanate, anion is towards water phase.But
Hydrophilic anion is connected directly with polyisocyanates, and cause-NCO group is readily accessible water and reacts, it reduces solid
The working life of agent, while generating carbon dioxide gas.Fluorine-containing polyether segment is by amphoteric ion and polyisocyanic acid in the present invention
Ester is spaced apart, and the fluorochemical polyether segment with strong hydrophobic effect can effectively cover and protect the-NCO base mutually closed on therewith
Group, the probability that reduction-NCO group is contacted and reacted with water are reduced solid to extend the working life of Water Dispersible Polyisocyanates
The chance for changing product release CO2 gas, improves the performance of dual-component aqueous polyurethane cured product.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment cross-reference.
The foregoing description of the disclosed embodiments makes professional and technical personnel in the field can be realized the present invention.To these
A variety of modifications of embodiment will be readily apparent to those skilled in the art, general original as defined herein
Reason can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will not
Be intended to be limited to the embodiments shown herein, and be to fit to it is consistent with the principles and novel features disclosed in this article most
Wide range.
Claims (10)
1. a kind of Water Dispersible Polyisocyanates composition, which is characterized in that include hydrophilically modified polyisocyanates curing agent
And aromatic polyisocyanate；Wherein, the mass ratio of hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate is
10:1~1:3, and NCO content is the 15~25% of the Water Dispersible Polyisocyanates composition gross mass, and this is water dispersible
Polyisocyantates composition contains fluorochemical polyether segment and amphoteric ion segment.
2. a kind of Water Dispersible Polyisocyanates composition according to claim 1, which is characterized in that the aromatic series is more
Isocyanates is the tripolymer or polymer derivative of aromatic diisocyanate and aromatic diisocyanate.
3. a kind of Water Dispersible Polyisocyanates composition according to claim 1, which is characterized in that the aromatic series is more
Isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene dimethylene diisocyanate, naphthalene diisocyanate
One of ester, tetramethylxylylene diisocyanate and polymeric diphenylmethane diisocyanate or a variety of mixing
Object.
4. a kind of Water Dispersible Polyisocyanates composition according to claim 1, which is characterized in that the hydrophilic modifying
The mass ratio of polyisocyanate curing agent and aromatic polyisocyanate is 5:1~1:1, and NCO content is the water dispersible polyisocyanate
The 17~23% of cyanate compositions gross mass.
5. a kind of Water Dispersible Polyisocyanates composition according to claim 1, which is characterized in that the hydrophilic modifying
Polyisocyanate curing agent, which is reacted by aliphatic or alicyclic polyisocyanates with fluorochemical polyether hydrophilic modifier, to be synthesized, and described
The quality of fluorochemical polyether hydrophilic modifier accounts for the 10.0~50.0% of the hydrophilically modified polyisocyanates curing agent gross mass, this contains
The molecular structural formula of perfluoroalkyl polyether hydrophilic modifier is as shown in formula A
Wherein, RfFor containing fluoroalkyl；R is alkyl；X is the integer of 1-20；Y is the integer of 1-20.
6. a kind of Water Dispersible Polyisocyanates composition according to claim 5, which is characterized in that
RfSpecially trifluoromethyl-CF3, pentafluoroethyl group-CH2CF3, four fluoropropyl-CH2CF2CF2H, perfluoro butyl-(CF2)3CF3、
Perfluoro hexyl-(CF2)5CF3, perfluoro capryl-(CF2)7CF3Or perfluoro hexyl ethyl-CH2CH2(CF2)5CF3；R is specially ethyl-
CH2CH3, propyl-CH2CH2CH3Or butyl-CH2CH2CH2CH3；X is the integer of 1-10；Y is the integer of 1-10.
7. a kind of Water Dispersible Polyisocyanates composition according to claim 6, which is characterized in that this is water dispersible more
Sulfonyl alkyl betaine group in isocyanate composition accounts for the 0.4~9.1% of gross mass, and the fluorochemical polyether is hydrophilic changes
The mass ratio of property agent accounts for the 2.5~45.5% of gross mass.
8. a kind of Water Dispersible Polyisocyanates composition according to claim 7, which is characterized in that this is water dispersible more
Sulfonyl alkyl betaine group in isocyanate composition accounts for the 1.4~6.6% of gross mass, and the fluorochemical polyether is hydrophilic changes
The mass ratio of property agent accounts for the 10.0~33.3% of gross mass.
9. a kind of preparation method of Water Dispersible Polyisocyanates composition, which is characterized in that be used to prepare in claim 1-8
Water Dispersible Polyisocyanates composition described in any claim, is prepared:
S1, synthesis hydrophilic modified polyisocyanate curing agent: fluorochemical polyether hydrophilic modifier is first synthesized；Then under nitrogen protection
Polyisocyanates is heated to 70-100 DEG C；Then fluorochemical polyether hydrophilic modifier is added into reactor, in catalyst dibutyltin
It is reacted in the presence of dilaurylate, wherein the quality of fluorochemical polyether hydrophilic modifier is polyisocyanates
The 5%-30% of quality, reaction temperature are 80-85 DEG C, reaction time 2.5-3-4h；Then chlorobenzoyl chloride is added and terminates reaction,
The quality of chlorobenzoyl chloride is the 0.01~0.1% of reactant gross mass；Stop reaction and obtains hydrophilically modified polyisocyanates solidification
Agent；
S2, under nitrogen protection, aromatic polyisocyanate is added in hydrophilically modified polyisocyanates curing agent, and stirring is mixed
5-40min is closed, obtains Water Dispersible Polyisocyanates composition, wherein hydrophilically modified polyisocyanates curing agent and aromatic series
The mass ratio of polyisocyanates is 10:1~1:3.
10. a kind of preparation method of Water Dispersible Polyisocyanates composition according to claim 9, which is characterized in that
The mass ratio of hydrophilically modified polyisocyanates curing agent and aromatic polyisocyanate is 5:1~1:1 in step S2, obtained
The dynamic viscosity of Water Dispersible Polyisocyanates composition be 4000mPa.s hereinafter, NCO content be gross mass 15~
25%.
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