CN104672422B - A kind of emulsifying agent synthesized suitable for aqueous polyurethane and its preparation method and application - Google Patents
A kind of emulsifying agent synthesized suitable for aqueous polyurethane and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of suitable for emulsifying agent of aqueous polyurethane synthesis and its preparation method and application.Existing patent is all to use prepolymer blend method, prepares aqueous polyurethane emulsion by resin alloy, does not suggest that exact emulsifying agent structure design, it is impossible to fully play the advantages of outer emulsification.The emulsifying agent of the present invention is using polyurethane resin as hydrophobic oleophilic oil segment, and using carboxylic acid alcohol, sulfamate, amino acid or hydroxy sulfonate as water-wet side compound, water-wet side is connected by being reacted with the isocyanic acid ester bond of hydrophobic oleophilic oil segment.The emulsifying agent of the present invention possesses the hydrophobic segment of polyurethane resin, using the teaching of the invention it is possible to provide better than common emulsifying agent and polyurethane system compatibility, so that providing stability is better than outer emulsion process aqueous polyurethane emulsion prepared by conventional emulsifier.
Description
Technical field
The present invention relates to aqueous polyurethane technical field, specifically a kind of emulsification suitable for aqueous polyurethane synthesis
Agent and its preparation method and application.
Background technology
Solvent borne polyurethane is widely used the surfacecti proteon in woodwork, adhesive, artificial leather because of its excellent performance
Deng field, but solvent borne polyurethane needs to add substantial amounts of volatile organic solvent in production, construction and solidification process, endangers
It is healthy and safe, environment is polluted.
In recent years, the harmfulness of volatile organic matter (VOC) in organic exhaust gas was all gradually paid attention in countries in the world, closed
It is increasingly severe in the regulation of control VOC, the clear stipulaties discharge species of organic matter, the discharge of part western developed country
Amount.Different from solvent borne polyurethane, for aqueous polyurethane using water as medium, water is not non-ignitable, quick-fried, nontoxic, tasteless, will not pollute ring
Border, and execution conditions are good, production and application safety, will not endanger construction and the health of operating personnel；Meanwhile water is cheap,
Be easy to get, therefore the cost of product can be significantly reduced, because and increasingly attracted people's attention.
According to the synthesis technique of aqueous polyurethane, internal emulsification method and outer emulsion process, breast prepared by outer emulsion process can be divided into
Liquid solid content is high, viscosity is dilute but stability is poor, therefore the production of most of aqueous polyurethane at present is using internal emulsification technique.
But common internal emulsification hydrophilic radical distribution is uncontrollable so as to which inevitably there are certain thickness hydration layer, oil phase and water phase
Boundary is not apparent from, and causes hydration thickness, solid content to be difficult to improve.How to ensure in the building-up process of aqueous polyurethane
Outer emulsification is realized on the premise of stability, is to improve that current internal emulsification aqueous polyurethane solid content, which is difficult to improve, viscosity is big has
Efficacious prescriptions method, but for this partial content, research is all fewer both at home and abroad.United States Patent (USP) US2004020847 and Chinese patent
The polyurethane resin that CN102093534A refer to coat not carboxylate-containing using the polyurethane of carboxylate-containing prepares water-based gather
Urethane lotion, CN102181032A prepare the hyperbranched water of response type using response type super branched polyurethane cladding base polyurethane prepolymer for use as
Property polyurethane film.But above-mentioned patent is all to use prepolymer blend method, and aqueous polyurethane emulsion is prepared by resin alloy, and
Exact emulsifying agent structure design is not proposed, it is impossible to fully plays the advantages of outer emulsification.
The content of the invention
Technical problem to be solved by this invention is to overcome the problems of the above-mentioned prior art, there is provided one kind is suitable for
The emulsifying agent of aqueous polyurethane synthesis, it is good with polyurethane resin compatibility that it has, and is easy in polyurethane resin microparticle surfaces point
Dissipate, and with characteristic that is reactive, not influencing finally film forming physical property.
For this reason, the present invention is realized by the following technical programs：A kind of emulsifying agent suitable for aqueous polyurethane synthesis,
It is characterized in that, the emulsifying agent is using polyurethane resin as hydrophobic oleophilic oil segment, with carboxylic acid alcohol, sulfamate, amino acid or hydroxyl
Base sulfonate is water-wet side compound, and water-wet side is connected by being reacted with the isocyanic acid ester bond of hydrophobic oleophilic oil segment, the emulsification
The structural formula of agent hydrophobic oleophilic oil segment is as shown in Equation 1,
In formula 1,
X is sealer；
For polymer diatomic alcohol；
OCN-NCO is diisocyanate.
The preparation method of the above-mentioned emulsifying agent suitable for aqueous polyurethane synthesis, it is characterised in that comprise the following steps：
1) by molar ratio 1:1 sealer stirs evenly under nitrogen protection with diisocyanate, in 60~90 DEG C of temperature
1.5~3h of lower reaction, obtains compound A；
2) by molar ratio 1:1 compound A is stirred evenly under nitrogen protection with polymer diatomic alcohol, in temperature 60~90
2.5~4h is reacted at DEG C, compound B is obtained, adds the diisocyanate with molar ratio with compound B, under nitrogen protection
Stir evenly, 2.5~4h is reacted at 60~90 DEG C of temperature, obtains compound C；
3) water-wet side compound and compound C are pressed into active function groups (such as OH or NH2) with the molar ratio 1 of NCO:1 adds,
Stir evenly under nitrogen protection, 2.5~4h is reacted at 60~90 DEG C of temperature, obtain being suitable for the breast of aqueous polyurethane synthesis
Agent.
The preparation method process of the present invention is simple, can be applied to property and requires aqueous polyurethane emulsion, high solids content
The preparation of aqueous polyurethane emulsion.
Further, the sealer be preferably methyl ethyl ketoxime, phenol, caprolactam, 2- pyridols, 3- oxyquinolines,
3,5- dimethyl pyrazoles, 1,2,4- triazole, in sodium hydrogensulfite, antifebrin, N- methylacetamides, diethyl ketone acryloyl amidoxime
One or more.
Further, the diisocyanate is preferably toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate
(IPDI), 2,4- ethylbenzene diisocyanate (EDI), Methylcyclohexyl diisocyanate (HTDI), 2,2,4- trimethyl cyclohexanes two
One or more in isocyanates (TMHDI).
Further, one or more of the polymer diatomic alcohol in polyether Glycols, polyester diol, preferably
For the one or more in the asymmetrical polyether Glycols of hydroxyl activity, polyester diol.
Further, the water-wet side compound is preferably dihydromethyl propionic acid, dimethylolpropionic acid, amino acid, second two
One or more in tarine sodium, second dihydroxy ethyl sulfonic acid sodium, malic acid, citric acid.
Another object of the present invention is to provide the application of mentioned emulsifier, it is characterised in that emulsifying agent is pre- with polyurethane
Aggressiveness in mass ratio 1:After 2~3.5 mixing, it is sufficiently stirred 15~300 seconds, obtains uniformly mixing performed polymer, adds and emulsify
The neutralizer that carboxylate radical molal quantity is suitable in agent neutralizes, and is then scattered in deionization under the high-speed stirred of 800~2000r/min
In water, the aqueous polyurethane colostric fluid of high solids is obtained；By its active function groups (such as OH or NH2) and aqueous polyurethane colostrum
NCO molar ratios are 0.01~0.8 in liquid:1 rear chain extender is added drop-wise in aqueous polyurethane colostric fluid, stirs 0.5~2h, decompression
The solvent in base polyurethane prepolymer for use as is sloughed, obtains the aqueous polyurethane emulsion of high solids.
The rear chain extender is preferably ethylenediamine, butanediamine, isophorone diamine, hexamethylene diamine, pentanediamine, piperazine, ring
Hexamethylene diamine, hydrazine, N, the one or more in N '-dimethyl ethylenediamine.
The neutralizer is preferably one kind in triethylamine, tri-n-butylamine, sodium hydroxide, diethanol amine, triethanolamine
It is or a variety of.
Further, the aqueous polyurethane emulsion film forming of obtained high solids, 130~150 DEG C dry 2~10min, potential
Blocked isocyanate functional group can further be reacted with polyurethane resin, improve the hardness and strength of film forming matter.
The preparation method of above-mentioned base polyurethane prepolymer for use as is as follows：
1) by the molecular weight of 50-80 mass parts for one kind in 500-4000 polymer diatomic alcohols or polymer polyatomic alcohol or
It is a variety of to be warming up to 90-120 DEG C, vacuum dehydration 30-90min, cool to after 55-75 DEG C and add the diisocyanate of 10-50 mass parts
Ester, stirs evenly under nitrogen protection, mixing time 0.5-1h, then adds two fourth of tin dilaurate of 0.01-0.2 mass parts
At least one of Ji Xi, stannous octoate are used as catalyst, react 1-3h at 60-90 DEG C, obtain the reactant of clear；
2) with 2,2- dihydromethyl propionic acids (DMPA), 2,2- dimethylolpropionic acids (DMBA), second diaminourea ethyl sulfonic acid sodium, second
At least one of dihydroxy ethyl sulfonic acid sodium is used as hydrophilic chain extender, with 1,4-butanediol, diglycol, 2- methyl-props two
In alcohol, 3- methyl pentanediols, neopentyl glycol, 1,6-HD, 2- methyl -2- ethyl glycols, trimethylolpropane at least
One kind is used as small molecule chain extender, with acetone, butanone, n,N-Dimethylformamide, 1-methyl-2-pyrrolidinone, N- ethyl pyrrolidines
At least one of ketone is used as solvent；By the hydrophilic chain extender of 0.5-5 mass parts, 1-15 mass parts small molecule chain extender,
The solvent of 0.1-50 mass parts is added in the reactant that step 1) obtains, and reacts 1-3h at 60-90 DEG C；Cool to 45-70
DEG C, obtain clarifying sticky base polyurethane prepolymer for use as.
In step 1), the diisocyanate is preferably toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate
(IPDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI), 4,4 ' one methylene, one or two hexamethylene
Group diisocyanate (H12MDI), xylylene diisocyanate (XDI), 2,2,4- trimethylhexane diisocyanates
(TMHDI) one or more in.The polymer diatomic alcohol is preferably polyethylene glycol adipate glycol, polyadipate fourth
Glycol esterdiol, polyhexamethylene adipate glycol, polyadipate diglycol esterdiol, polyneopentyl glycol adipate
One or more in glycol, polycaprolactone glycol, poly- carbonic acid hexylene glycol esterdiol, polyoxypropylene, polytetrahydrofuran ether.
The advantages of emulsifying agent of the present invention, is：Emulsifying agent possesses that compatibility is good, stability is good and the later stage is reactive excellent
Point.Emulsifying agent possesses the hydrophobic segment of polyurethane resin, using the teaching of the invention it is possible to provide compatible better than common emulsifying agent and polyurethane system
Property, so that providing stability is better than outer emulsion process aqueous polyurethane emulsion prepared by conventional emulsifier.Emulsifying agent possess it is potential can
The blocked isocyanate functional group of reaction, can further be crosslinked in application baking process, eliminate small-molecule substance to film forming
The influence of overall physical property.
Embodiment
Illustrate the present invention, but the present invention is not restricted to these example below by way of specific embodiment.
Embodiment 1
1mol methyl ethyl ketoximes and 1mol toluene di-isocyanate(TDI)s are stirred evenly under nitrogen protection, it is anti-at 90 DEG C of temperature
1.5h is answered, obtains compound A；The polypropylene glycol of 2000 molecular weight of 1mol is added and stirred evenly under nitrogen protection, in temperature
4h is reacted at 60 DEG C of degree, compound B is obtained, adds 1mol Methylcyclohexyl diisocyanates, stirring is equal under nitrogen protection
It is even, 4h is reacted under temperature 60 C, obtains compound C；0.5mol dihydromethyl propionic acids are added, stirring is equal under nitrogen protection
It is even, 2.5h is reacted at 90 DEG C of temperature, obtains the emulsifying agent for being adapted to aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 500 molecular weight of 50g at 110 DEG C, vacuum dehydration 1.5h, cools to 65
DEG C, 39g TDI are added, under nitrogen protection, 0.5h is stirred, adds dibutyl tin laurate 0.015g, at 80 DEG C, reaction
2h；Addition 1g DMPA, 1g 1,4-butanediol, 2g neopentyl glycols, 10g butanone, 5g 1-methyl-2-pyrrolidinones, at 80 DEG C, instead
3h is answered, cools to 50 DEG C, the sticky performed polymer A of clear is obtained, 50g emulsifying agents and 100g performed polymers A is uniformly mixed, added
Enter and neutralized with contained dihydromethyl propionic acid in emulsifying agent with the triethylamine of molar ratio, under the high-speed stirred of 800~2000r/min
It is scattered in 150g deionized waters, adds chain extension after 3g ethylenediamines, stir 1h, decompression sloughs solvent, obtains the water of high solids
Property polyaminoester emulsion.
Embodiment 2
1mol caprolactams and 1mol toluene di-isocyanate(TDI)s are stirred evenly under nitrogen protection, it is anti-under temperature 60 C
3h is answered, obtains compound A；The poly- neopentyl glycol ester of 2000 molecular weight of 1mol is added and stirred evenly under nitrogen protection,
2.5h is reacted at 90 DEG C of temperature, obtains compound B, adds 1mol 2,4- ethylbenzene diisocyanate, is stirred under nitrogen protection
Uniformly, 2.5h is reacted at 90 DEG C of temperature, obtains compound C；1mol malic acid is added, is stirred evenly under nitrogen protection,
4h is reacted under temperature 60 C, obtains the emulsifying agent for being adapted to aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 500 molecular weight of 50g at 110 DEG C, vacuum dehydration 1.5h, cools to 65
DEG C, 50g IPDI are added, under nitrogen protection, 0.5h is stirred, adds stannous octoate 0.02g, at 80 DEG C, react 2h；Add 2g
Second dihydroxy ethyl sulfonic acid sodium, 3g 2- methyl propanediols, 2g 3- methyl pentanediols, 10g butanone, 5g 1-methyl-2-pyrrolidinones,
At 80 DEG C, 3h is reacted, 50 DEG C is cooled to, obtains the sticky performed polymer A of clear, 30g emulsifying agents and 100g performed polymers A are mixed
Close uniform, add and neutralized with contained malic acid in emulsifying agent with the triethylamine of 2 times of molar ratio, in the high speed of 800~2000r/min
It is scattered under stirring in 100g deionized waters, adds chain extension after 2g hexamethylene diamines, stir 1h, decompression sloughs solvent, obtains Gao Hangu
The aqueous polyurethane emulsion of amount.
Embodiment 3
By 1mol 3,5- dimethyl pyrazoles stir evenly under nitrogen protection with 1mol isophorone diisocyanate,
1.5h is reacted at 90 DEG C of temperature, obtains compound A；The polypropylene glycol of 1000 molecular weight of 1mol is added simultaneously under nitrogen protection
Stir evenly, react 4h under temperature 60 C, obtain compound B, add 1mol toluene di-isocyanate(TDI)s, under nitrogen protection
Stir evenly, react 4h under temperature 60 C, obtain compound C；0.5mol dimethylolpropionic acids are added, under nitrogen protection
Stir evenly, react 2.5h at 90 DEG C of temperature, obtain the emulsifying agent for being adapted to aqueous polyurethane synthesis.
By the polypropylene glycol of 2000 molecular weight of 150g, 50g polyether polyol N330 is at 110 DEG C, vacuum dehydration 1h, drop
Temperature adds 40g IPDI to 65 DEG C, and 30gHDI, under nitrogen protection, stirs 0.5h, add 0.15g stannous octoates, at 80 DEG C,
React 2h；6g diglycols are added, 2g trimethylolpropanes, 30g acetone, at 70 DEG C, reacts 3h, cools to 45 DEG C,
The sticky performed polymer A of clear is obtained, 50g emulsifying agents and 120g performed polymers A are uniformly mixed, it is contained in addition and emulsifying agent
Dimethylolpropionic acid is neutralized with the triethylamine of molar ratio, and 150g deionizations are scattered under the high-speed stirred of 800~2000r/min
In water, chain extension after 8g butanediamine is added, stirs 1h, decompression sloughs solvent, obtains the aqueous polyurethane emulsion of high solids.
Embodiment 4
1mol sodium hydrogensulfites and 1mol toluene di-isocyanate(TDI)s are stirred evenly under nitrogen protection, at 90 DEG C of temperature
1.5h is reacted, obtains compound A；The polypropylene glycol of 2000 molecular weight of 1mol is added and stirred evenly under nitrogen protection,
4h is reacted under temperature 60 C, obtains compound B, adds 2,2,4- trimethylhexane diisocyanates of 1mol, is protected in nitrogen
Under stir evenly, react 4h under temperature 60 C, obtain compound C；0.5mol dihydromethyl propionic acids are added, are protected in nitrogen
Under stir evenly, react 2.5h at 90 DEG C of temperature, obtain the emulsifying agent for being adapted to aqueous polyurethane synthesis.
By the polybutylene glyool adipate of 500 molecular weight of 50g at 110 DEG C, vacuum dehydration 1.5h, cools to 65
DEG C, 20g TDI, 18g TDHDI are added, under nitrogen protection, 0.5h is stirred, dibutyl tin laurate 0.015g is added, 80
At DEG C, 2h is reacted；Addition 0.5g DMBA, 5g 1,6- hexylene glycols, 10g butanone, 5g N- ethyl pyrrolidones, at 80 DEG C, instead
3h is answered, cools to 50 DEG C, the sticky performed polymer A of clear is obtained, 50g emulsifying agents and 100g performed polymers A is uniformly mixed, added
Enter and neutralized with contained dihydromethyl propionic acid in emulsifying agent with the triethylamine of molar ratio, under the high-speed stirred of 800~2000r/min
It is scattered in 150g deionized waters, adds chain extension after 3.5g cyclohexanediamine diamines, stir 1h, decompression sloughs solvent, obtains height and contain
Admittedly the aqueous polyurethane emulsion measured.
Embodiment 5
1mol N- methylacetamides and 1mol isophorone diisocyanate are stirred evenly under nitrogen protection, in temperature
3.5h is reacted at 90 DEG C of degree, obtains compound A；The polypropylene glycol of 2000 molecular weight of 1mol is added and stirred under nitrogen protection
Mix uniformly, react 4h under temperature 60 C, obtain compound B, add 1mol toluene di-isocyanate(TDI)s, stir under nitrogen protection
Mix uniformly, react 4h under temperature 60 C, obtain compound C；1mol citric acids are added, are stirred evenly under nitrogen protection,
2.5h is reacted at 90 DEG C of temperature, obtains the emulsifying agent for being adapted to aqueous polyurethane synthesis.
By the polytetrahydrofuran ether glycol of 2000 molecular weight of 200g at 110 DEG C, vacuum dehydration 1h, cools to 65 DEG C, adds
Enter 44.6g IPDI, under the protection of 15g H12MDI nitrogen, stir 0.5h, add 0.18g stannous octoates, at 80 DEG C, react 2h；
1g 1,4-butanediol is added, 2g neopentyl glycols, 10g butanone, 5g DMF, at 80 DEG C, react 3h, cool to 50 DEG C, obtain clear
Clear bright sticky performed polymer A, 30g emulsifying agents and 100g performed polymers A are uniformly mixed, and are added and contained citric acid in emulsifying agent
The triethylamine of 3 times of molar ratios neutralizes, and is scattered under the high-speed stirred of 800~2000r/min in 90g deionized waters, adds 5g
Chain extension after isophorone diamine, stirs 1h, and decompression sloughs solvent, obtains the aqueous polyurethane emulsion of high solids.
Embodiment 6
0.5mol phenol, 0.5mol diethyl ketone acryloyl amidoximes and 1mol toluene di-isocyanate(TDI)s are stirred under nitrogen protection
Mix uniformly, react 2.5h at 90 DEG C of temperature, obtain compound A；The poly adipate succinic acid ester of 1000 molecular weight of 1mol is existed
Add and stir evenly under nitrogen protection, react 4h under temperature 60 C, obtain compound B, add 1mol isophorones two
Isocyanates, stirs evenly under nitrogen protection, reacts 4h under temperature 60 C, obtains compound C；By 0.5mol second diaminourea
Ethyl sulfonic acid sodium adds, and stirs evenly under nitrogen protection, reacts 2.5h at 90 DEG C of temperature, obtains being adapted to aqueous polyurethane synthesis
Emulsifying agent.
By the polytetrahydrofuran ether glycol of 2000 molecular weight of 200g at 110 DEG C, vacuum dehydration 1h, cools to 65 DEG C, adds
Enter 43.5g XDI, under the protection of 29g MDI nitrogen, stir 0.5h, add 0.1g stannous octoates, at 80 DEG C, react 2h；Add
1g 2- methyl -2- ethyl glycols, 2.5g 3- methyl pentanediols, 10g butanone, 5g 1-methyl-2-pyrrolidinones, at 80 DEG C,
3h is reacted, 50 DEG C is cooled to, obtains the sticky performed polymer A of clear, 50g emulsifying agents and 100g performed polymers A are uniformly mixed,
It is scattered under the high-speed stirred of 800~2000r/min in 150g deionized waters, adds 1g pentanediamines, 3g N, N '-dimethyl
Chain extension after ethylenediamine, stirs 1h, and decompression sloughs solvent, obtains the aqueous polyurethane emulsion of high solids.
Claims (8)
1. a kind of emulsifying agent suitable for aqueous polyurethane synthesis, it is characterised in that the emulsifying agent is using polyurethane resin to be hydrophobic
Oleophylic segment, using sulfamate or hydroxy sulfonate as water-wet side compound, water-wet side passes through different with hydrophobic oleophilic oil segment
Cyanic acid ester bond is reacted and connected, and the structural formula of the emulsifying agent hydrophobic oleophilic oil segment is as shown in Equation 1,
In formula 1,
X is sealer；
For polymer diatomic alcohol；
The sealer for methyl ethyl ketoxime, phenol, caprolactam, 2- pyridols, 3- oxyquinolines, 3,5- dimethyl pyrazoles,
One or more in 1,2,4- triazoles, sodium hydrogensulfite, antifebrin, N- methylacetamides, diethyl ketone acryloyl amidoxime；
The water-wet side compound is dihydromethyl propionic acid, dimethylolpropionic acid, second diaminourea ethyl sulfonic acid sodium, second dihydroxy second
One or more in sodium sulfonate.
2. the preparation method of emulsifying agent described in claim 1, it includes following steps：
1) by molar ratio 1:1 sealer stirs evenly under nitrogen protection with diisocyanate, anti-at 60~90 DEG C of temperature
1.5~3h is answered, obtains compound A；
2) by molar ratio 1:1 compound A is stirred evenly under nitrogen protection with polymer diatomic alcohol, at 60~90 DEG C of temperature
2.5~4h is reacted, compound B is obtained, adds the diisocyanate with molar ratio with compound B, stir under nitrogen protection
Uniformly, 2.5~4h is reacted at 60~90 DEG C of temperature, obtains compound C；
3) water-wet side compound and compound C are pressed into active function groups and the molar ratio 1 of NCO:1 adds, and stirs under nitrogen protection
Mix uniformly, 2.5~4h is reacted at 60~90 DEG C of temperature, obtain being suitable for the emulsifying agent of aqueous polyurethane synthesis.
3. preparation method according to claim 2, it is characterised in that the diisocyanate is toluene diisocynate
Ester, isophorone diisocyanate, 2,4- ethylbenzene diisocyanate, Methylcyclohexyl diisocyanate, 2,2,4- trimethyls oneself
One or more in alkane diisocyanate.
4. preparation method according to claim 2, it is characterised in that the polymer diatomic alcohol is selected from polyethers binary
One or more in alcohol, polyester diol.
5. preparation method according to claim 4, it is characterised in that it is non-that the polymer diatomic alcohol is selected from hydroxyl activity
One or more in symmetrical polyether Glycols, polyester diol.
6. the application of emulsifying agent described in claim 1, it is characterised in that by emulsifying agent and base polyurethane prepolymer for use as in mass ratio 1:2
After~3.5 mixing, it is sufficiently stirred 15~300 seconds, obtains uniformly mixing performed polymer, adds and carboxylate radical molal quantity in emulsifying agent
Suitable neutralizer neutralizes, and is then scattered under the high-speed stirred of 800~2000r/min in deionized water, obtains Gao Hangu
The aqueous polyurethane colostric fluid of amount；It is 0.01~0.8 by NCO molar ratios in its active function groups and aqueous polyurethane colostric fluid:1
Rear chain extender be added drop-wise in aqueous polyurethane colostric fluid, stir 0.5~2h, solvent in base polyurethane prepolymer for use as is sloughed in decompression,
Obtain the aqueous polyurethane emulsion of high solids.
7. application according to claim 6, it is characterised in that the aqueous polyurethane emulsion film forming of obtained high solids,
130~150 DEG C of 2~10min of drying.
8. application according to claim 6, it is characterised in that the preparation method of above-mentioned base polyurethane prepolymer for use as is as follows：
1) it is one kind or more in 500~4000 polymer diatomic alcohols or polymer polyatomic alcohol by the molecular weight of 50~80 mass parts
Kind is warming up to 90~120 DEG C, 30~90min of vacuum dehydration, cools to after 55~75 DEG C and adds two isocyanides of 10~50 mass parts
Acid esters, stirs evenly under nitrogen protection, and mixing time is 0.5~1h, then adds the tin dilaurate of 0.01~0.2 mass parts
At least one of dibutyl tin, stannous octoate are used as catalyst, and 1~3h is reacted at 60~90 DEG C, obtains the anti-of clear
Answer thing；
2) with 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids, second diaminourea ethyl sulfonic acid sodium, second dihydroxy ethyl sulfonic acid sodium
At least one as hydrophilic chain extender, with 1,4-butanediol, diglycol, 2- methyl propanediols, 3- methyl pentanediols,
At least one of neopentyl glycol, 1,6-HD, 2- methyl -2- ethyl glycols, trimethylolpropane expand as small molecule
Chain agent, is made with least one of acetone, butanone, n,N-Dimethylformamide, 1-methyl-2-pyrrolidinone, N- ethyl pyrrolidones
For solvent；By the hydrophilic chain extender of 0.5~5 mass parts, the small molecule chain extender of 1~15 mass parts, 0.1~50 mass parts it is molten
Agent is added in the reactant that step 1) obtains, and 1~3h is reacted at 60~90 DEG C；45~70 DEG C are cooled to, it is viscous to obtain clarification
Thick base polyurethane prepolymer for use as.
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| CN106543402B (en) * | 2016-10-21 | 2019-11-26 | 杭州传化精细化工有限公司 | A kind of preparation method of cross-linking block-graft type high molecular polymer |
| CN108484862A (en) * | 2018-04-11 | 2018-09-04 | 肇庆市华莱特复合新型材料有限公司 | A kind of aqueous polyurethane dispersion and preparation method thereof |
| CN115403730B (en) * | 2022-10-13 | 2023-06-27 | 江苏四新界面剂科技有限公司 | Food white oil emulsifier and preparation method thereof |
| CN115926105A (en) * | 2022-12-30 | 2023-04-07 | 佛山市精信汇明科技有限公司 | Reactive polyurethane anionic-nonionic emulsifier and preparation method and application thereof |
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| US5189133A (en) * | 1991-02-27 | 1993-02-23 | Bayer Aktiengesellschaft | Hydrophylic, olefinically unsaturated polyurethanes and their use as reactive emulsifiers |
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| US5189133A (en) * | 1991-02-27 | 1993-02-23 | Bayer Aktiengesellschaft | Hydrophylic, olefinically unsaturated polyurethanes and their use as reactive emulsifiers |
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