CN108178824A - A kind of sulfonic waterborne polyurethane emulsion and its non-solvent preparation - Google Patents
A kind of sulfonic waterborne polyurethane emulsion and its non-solvent preparation Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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Abstract
The present invention provides a kind of sulfonic waterborne polyurethane emulsion and its non-solvent preparation, belongs to aqueous polyurethane synthesis field of new materials.This method first adds in diisocyanate, polymer diatomic alcohol, antioxidant, catalyst, small molecule dihydric alcohol and hydrophilic chain extender in temperature of reaction kettle, obtains the first intermediate；Then the first intermediate is put into the second reaction kettle, adds in sulfonate type polyamine hydrophilic chain extender, obtain the second intermediate；Small molecule dihydric alcohol is added in into the second intermediate, obtains third intermediate；Third intermediate is added in third dispersion reaction kettle, deionized water and neutralizer is added in, obtains sulfonic waterborne polyurethane emulsion.The present invention also provides a kind of sulfonic waterborne polyurethane emulsions.The molecular weight for the aqueous polyurethane that the present invention obtains is higher, has excellent mechanical performance, and the elongation at break of aqueous polyurethane can be up to 630 1020%, and tensile strength is up to 55 68MPa.
Description
Technical field
The invention belongs to aqueous polyurethane synthesis field of new materials more particularly to a kind of sulfonic waterborne polyurethane emulsion and
Its non-solvent preparation.
Background technology
Aqueous polyurethane is a kind of using water as decentralized medium, in the production and use process without volatility and toxicity
Larger " pentaphene, three aldehyde ", not can cause environmental pollution, will not damage to operator's health, have nontoxic, nothing
Taste, it is non-ignitable, it is not quick-fried, it is safe the characteristics of.Traditional aqueous polyurethane is mostly carboxylic acid type aqueous polyurethane, however, such is aqueous
Polyurethane the problem is that high solids content is relatively difficult to synthesize, and water dispersible excellent in order to obtain, generally require plus
The carboxylic acid type hydrophilic chain extender entered is more than 6.5%, necessarily water resistance is caused to be deteriorated in this way.Sulfonic acid type water-based polyurethane often contains
Amino group so during the reaction, generally requires to add in a large amount of inert diluent, can not only increase organic solvent in this way
Additive amount, and reaction efficiency can be reduced.
No-solvent process prepares aqueous polyurethane emulsion, also all arrived in recent years some research, in order to make reacting balance into
Row generally requires to improve reaction temperature, however, the raising of reaction temperature, after sulfonate can be caused to add in, leads to product gel,
It can not obtain product.
Invention content
The purpose of the present invention is to solve existing no-solvent process to prepare sulfonate existing for aqueous polyurethane emulsion
The problem of can not adding in, influence properties of product, and a kind of sulfonic waterborne polyurethane emulsion and its non-solvent preparation are provided.
Present invention firstly provides a kind of non-solvent preparations of sulfonic waterborne polyurethane emulsion, comprise the following steps：
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 140~240 DEG C, adds in diisocyanate, polymer
Dihydric alcohol, antioxidant, catalyst, small molecule dihydric alcohol and hydrophilic chain extender, melting are stirred 15-90min, are obtained among first
Body；
Step 2：The first intermediate that step 1 obtains is put into the second reaction kettle, the temperature control of the second reaction kettle
Then system adds in sulfonate type polyamine hydrophilic chain extender at 60-75 DEG C, reaction time 5-10min is obtained among second
Body；
Step 3: adding in small molecule dihydric alcohol into the second intermediate that step 2 obtains, temperature is increased to 160-240
DEG C, 15-30min is reacted, obtains third intermediate；
Step 4: the third intermediate that step 3 obtains is added in third dispersion reaction kettle, reaction temperature control exists
30~50 DEG C, deionized water and neutralizer are then added in, 30-180min is reacted, obtains sulfonic waterborne polyurethane emulsion.
Preferably, the diisocyanate is selected from 4,4- '-diphenylmethane diisocyanates, toluene di-isocyanate(TDI), benzene
Methylene diisocyanate, 1,5- how diisocyanate, paraphenylene diisocyanate, hexamethylene diisocyanate, different Buddhist diketone
One or more of diisocyanate, hydrogenation 4,4- '-diphenylmethane diisocyanates.
Preferably, the one kind of the polymer diatomic alcohol in polyether Glycols or polyester diol.
Preferably, the polyether Glycols are selected from PolyTHF dihydric alcohol, Polyoxypropylene diol or polyoxy
Change one kind of ethylene dihydric alcohol, molecular weight 2000-5000Da, the water content of polyether Glycols is in below 300ppm.
Preferably, the polyester diol is selected from polyadipate-Isosorbide-5-Nitrae butyl glycol ester diol, polyadipate ethylene glycol
Esterdiol, polypropylene glycol adipate glycol, polyneopentyl glycol adipate glycol, polyadipate hexylene glycol neopentyl glycol ester two
Alcohol or gather own Inner esterdiols in one kind, molecular weight ranges 2000-5000, polyester diol water content 300ppm with
Under.
Preferably, the antioxidant is selected from model Irganox1010, Irgafos of BASF AG's production
One kind in 168 or Irganox 1076.
Preferably, the hydrophilic chain extender is one kind in dihydromethyl propionic acid or dimethylolpropionic acid.
Preferably, the sulfonate type polyamine hydrophilic chain extender is 2- [(2- amino-ethyls) amino] ethanesulfonic acid sodium
Salt, 2,4- diamino benzene sulfonic acids sodium or 3- (five poly- (1- (ammonia propoxyl group) propyl) amino) propyl -1- sodium sulfonates.
Preferably, the diisocyanate, polymer diatomic alcohol, antioxidant, catalyst, small molecule dihydric alcohol, parent
Water chain extender, sulfonate type polyamine hydrophilic chain extender, deionized water and neutralizer weight ratio be (20-30)：(80-120)：
(0.3-0.5)：(0.05-0.1)：(2.5-4.2)：(2.8-4.5)：(0.4-1.2)：(110-170)：(4.5-7.2).
The present invention also provides the sulfonic waterborne polyurethane emulsions that above-mentioned preparation method obtains.
Beneficial effects of the present invention
1) present invention provides a kind of non-solvent preparation of aqueous polyurethane emulsion, and the preparation process is by adding in sulfonic acid
Salt hydrophilic chain extender reduces hydrophile content, improves the water resistance of water-base resin.
2) present invention reduces reaction temperature during hydrophilic chain extender addition, it ensure that the smooth polymerization of product, complete
The synthesis of solvent-free sulfonic acid type water-based polyurethane.
3) molecular weight for the aqueous polyurethane that the preparation process obtains is higher, has excellent mechanical performance, aqueous poly- ammonia
The elongation at break of ester can be up to 630-1020%, and tensile strength is up to 55-68MPa.
Specific embodiment
The present invention provides a kind of solventless method preparation method of aqueous polyurethane emulsion, comprises the following steps：
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 140~240 DEG C, adds in diisocyanate, polymer
Dihydric alcohol, antioxidant, catalyst, small molecule dihydric alcohol and hydrophilic chain extender, melting are stirred 15-90min, are obtained among first
Body；
Step 2：The first intermediate that step 1 obtains is put into the second reaction kettle, the temperature control of the second reaction kettle
Then system adds in sulfonate type polyamine hydrophilic chain extender at 60-75 DEG C, reaction time 5-10min is obtained among second
Body；
Step 3: adding in small molecule dihydric alcohol into the second intermediate that step 2 obtains, temperature is increased to 160-240
DEG C, 15-30min is reacted, obtains third intermediate；
Step 4: the third intermediate that step 3 obtains is added in third dispersion reaction kettle, reaction temperature control exists
30~50 DEG C, deionized water and neutralizer are then added in, 30-180min is reacted, obtains sulfonic waterborne polyurethane emulsion.
According to the present invention, the diisocyanate is preferably selected from 4,4- '-diphenylmethane diisocyanates (MDI), toluene two
Isocyanates (TDI), tolylene diisocyanate (XDI), 1,5- how diisocyanate (NDI), paraphenylene diisocyanate
(PPDI), hexamethylene diisocyanate (HDI), different Buddhist diisocyanates
(IPDI), hydrogenation 4,4- '-diphenylmethane diisocyanates (H12One or more of MDI).
According to the present invention, the one kind of the polymer diatomic alcohol in polyether Glycols or polyester diol.It is described
Polyether Glycols be preferably selected from the one of PolyTHF dihydric alcohol, Polyoxypropylene diol or polyoxyethylene glycol
Kind, molecular weight 2000-5000Da, and the moisture of the polyether Glycols is in below 300ppm；Since sulfonate type is more
The addition of first amine hydrophilic chain extender increases the hardness of entire strand, thus, it is desirable that polymer polyatomic alcohol molecular weight ranges compared with
It is small, otherwise will appear the problem of cold bonding is hot-short, when molecular weight be less than 2000Da when, obtained product is more crisp, tensile strength compared with
Greatly, but elongation at break is smaller, and water-base resin is disconnected once drawing；When molecular weight is higher than 5000Da, obtained aqueous polyurethane
Elongation at break it is bigger, but tensile strength is too small, it is impossible to meet and use；So the present invention will strictly control polyethers two
The molecular weight of first alcohol when molecular weight is smaller and larger, can all influence the mechanical performance of water-base resin.
According to the present invention, the polyester diol is preferably selected from polyadipate-Isosorbide-5-Nitrae butyl glycol ester diol, polyadipate
Glycol ester glycol, polypropylene glycol adipate glycol, polyneopentyl glycol adipate glycol, polyadipate hexylene glycol new penta 2
One kind in alcohol esterdiol or poly- own Inner esterdiols, molecular weight ranges 2000-5000Da, and the polyester diol water
Divide in 300ppm hereinafter, when molecular weight is less than 2000Da, obtained product is more crisp, and tensile strength is larger, but fracture is stretched
Long rate is smaller, and water-base resin is disconnected once drawing；When molecular weight is higher than 5000Da, the elongation at break ratio of obtained aqueous polyurethane
It is larger, but tensile strength is too small, it is impossible to meet and use；So the present invention will strictly control the molecular weight of polyether Glycols,
When molecular weight is smaller and larger, the mechanical performance of water-base resin can be all influenced.
According to the present invention, the antioxidant be preferably selected from BASF AG production model Irganox1010,
One kind in Irgafos 168 or Irganox 1076.The present invention is glued by improving reaction temperature with reducing in polymerization process
High problem is spent, avoids the use of atent solvent, in order to avoid what is decomposed due to the excessively high caused polyurethane of reaction temperature
Risk adds in antioxidant to solve the problems, such as this.The effect of antioxidant of the present invention is to protect aqueous polyurethane structure at high temperature
Decomposition is will not be oxidized, the high-temperature oxydation of high molecular material resolves into small point mainly due to the effect of the oxygen in air
Son, the effect of antioxidant are that at high temperature, the oxygen around macromolecule is adsorbed by antioxidant, so as to protect aqueous polyurethane
Material will not be oxidized decomposition.
According to the present invention, it is pungent that the catalyst is preferably selected from stannous octoate, dibutyl tin laurate, tin dilaurate two
Base tin or Bismuth Octoate.The small molecule dihydric alcohol is preferably selected from ethylene glycol, 1,3- propylene glycol, 1,4- butanediols, 1,5- penta 2
One kind in alcohol, 1,6- hexylene glycols or cyclohexane dimethanol, small molecule dihydric alcohol moisture is in below 300ppm.The hydrophilic expansion
Chain agent is preferably one kind in dihydromethyl propionic acid or dimethylolpropionic acid；The neutralizer is preferably selected from triethylamine or N,
One kind in N- dimethylethanolamines.
According to the present invention, the sulfonate type polyamine hydrophilic chain extender is preferably 2- [(2- amino-ethyls) amino] second sulphur
Acid sodium-salt, 2,4- diamino benzene sulfonic acids sodium or 3- (five poly- (1- (ammonia propoxyl group) propyl) amino) propyl -1- sodium sulfonates.Sulfonate
The acting as of type polyamine hydrophilic chain extender introduces hydrophilic radical in polyurethane backbone structure, ensure that polyurethane can disperse
In water, so as to prepare aqueous polyurethane, and compared with carboxylic acid type hydrophilic chain extender, sulfonic acid type hydrophilic chain extender category strong acid
Highly basic salt has stronger hydrophily, and degree of ionization is high, can freely dissociate in water, form stronger Coulomb force, intermolecular
Active force is strong, generates very strong electrostatic interaction effect, the aqueous polyurethane to be formed micelle is promoted to be stably dispersed in water,
With superior storage stability, dispersion has more stable " electric double layer " structure, and comprehensive performance is more excellent.
According to the present invention, the diisocyanate, polymer diatomic alcohol, antioxidant, catalyst, small molecule dihydric alcohol,
Hydrophilic chain extender, sulfonate type polyamine hydrophilic chain extender, deionized water and neutralizer weight ratio be preferably (20-30)：
(80-120)：(0.3-0.5)：(0.05-0.1)：(2.5-4.2)：(2.8-4.5)：(0.4-1.2)：(110-170)：(4.5-
7.2)。
In step 1 of the present invention should stringent controlling reaction temperature, the reaction temperature be 140~240 DEG C, preferably
160~220 DEG C, when reaction temperature is less than less than 140 DEG C, prepolymer viscosity is excessive so that reaction is difficult to stir evenly, and causes
Product is unstable；, can be excessively high due to temperature when reaction temperature is higher than 240 DEG C or more, even if in the presence of having antioxidant,
Also can product further be degraded so that molecular weight product substantially reduces, and can not obtain qualified products.
Temperature control needs to control at 60-75 DEG C in step 2 of the present invention, and when reaction temperature is higher than 75 DEG C, reaction is too fast,
It can lead to product gel, reaction temperature is less than 60 DEG C, then reaction speed is excessively slow, influences production efficiency.
The present invention also provides the sulfonic waterborne polyurethane emulsions that above-mentioned preparation method obtains.
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than restriction protection scope of the present invention.
Embodiment 1
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 140 DEG C, adds in 4,4- diphenyl-methanes, two isocyanide of 20g
Acid esters, the tetrahydrofuran dihydric alcohol (Mn=1000) of 80g, 0.3g Irganox1010,0.05g stannous octoate and 2.8g
Dihydromethyl propionic acid, melting stir 90min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 60 DEG C, is added in
2- [(2- amino-ethyls) amino] b sodium salt of 0.4g, reaction time 10min obtain the second intermediate；
Step 3: adding in the ethylene glycol of 2.5g into the second intermediate, temperature is increased to 160 DEG C, reacts 30min, obtains
Third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 30 DEG C, is added
Enter the deionized water of 110g and the triethylamine of 4.5g, react, the reaction time is preferably 180min, obtains aqueous poly- ammonia
Ester lotion.
The aqueous polyurethane that embodiment 1 obtains is labeled as WPU-1, and the performance test results are as shown in Tables 1 and 2.
Embodiment 2
Step 1：Nitrogen protection under, temperature of reaction kettle is increased to 240 DEG C, add in 30g toluene di-isocyanate(TDI),
The Polyoxypropylene diol (Mn=8000) of 120g, the Irgafos 168 of 0.5g, 0.1g dibutyl tin laurate and
The dimethylolpropionic acid of 4.5g, melting stir 15min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 75 DEG C, is added in
2, the 4- diamino benzene sulfonic acid sodium of 1.2g, reaction time 5min obtain the second intermediate；
Step 3: adding in the 1,3-PD of 4.2g into the second intermediate, temperature is increased to 240 DEG C, reacts 15min,
Obtain third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 50 DEG C, is added
Enter the deionized water of 170g and the N of 7.2g, N- dimethylethanolamine, react 30min, obtain aqueous polyurethane emulsion.
The aqueous polyurethane that embodiment 2 obtains is labeled as WPU-2, and the performance test results are as shown in Tables 1 and 2.
Embodiment 3
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 160 DEG C, adds in the benzylidene diisocyanate of 25g
Ester, the polyoxyethylene glycol (Mn=3000) of 100g, the Irganox 1076 of 0.4g, the Bismuth Octoate of 0.08g and 3.0g
Dihydromethyl propionic acid, melting stir 25min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 65 DEG C, is added in
3- (five poly- (1- (ammonia propoxyl group) propyl) amino) propyl -1- sodium sulfonates of 0.6g, reaction time 8min are obtained among second
Body；
Step 3: adding in the 1,4-butanediol of 3g into the second intermediate, temperature is increased to 180 DEG C, reacts 20min, obtains
To third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 40 DEG C, so
The deionized water of 130g and the triethylamine of 5.2g are added in afterwards, are reacted 60min, are obtained aqueous polyurethane emulsion.
The aqueous polyurethane that embodiment 3 obtains is labeled as WPU-3, and the performance test results are as shown in Tables 1 and 2.
Embodiment 4
Step 1：Nitrogen protection under, temperature of reaction kettle is increased to 180 DEG C, add in 24g 1,5- how diisocyanate,
- 1,4 butyl glycol ester diol of polyadipate (Mn=5000) of 95g, the bismuth neodecanoate of Irganox1010,0.06g of 0.35g and
The dimethylolpropionic acid of 3.2g, melting stir 60min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 70 DEG C, is added in
2- [(2- amino-ethyls) amino] b sodium salt of 1.0g, reaction time 6min obtain the second intermediate；
Step 3: adding in the small molecule 1 of 3.5g into the second intermediate, 6- hexylene glycols, temperature is increased to 200 DEG C, reaction
25min obtains third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 35 DEG C, so
The deionized water of 150g is added in afterwards and the N of 6.2g, N- dimethylethanolamines react 90min, obtain aqueous polyurethane emulsion.
The aqueous polyurethane that embodiment 4 obtains is labeled as WPU-4, and the performance test results are as shown in Tables 1 and 2.
Embodiment 5
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 200 DEG C, adds in the hexa-methylene diisocyanate of 28g
Ester, the polyethylene glycol adipate glycol (Mn=2000) of 110g, the Irgafos 168 of 0.45g, 0.08g Bismuth Octoate and
The dihydromethyl propionic acid of 4.0g, melting stir 80min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 68 DEG C, is added in
2- [(2- amino-ethyls) amino] b sodium salt of 0.8g, reaction time 10min obtain the second intermediate；
Step 3: adding in the cyclohexane dimethanol of 4g into the second intermediate, temperature is increased to 200 DEG C, reacts 20min,
Obtain third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 45 DEG C, so
The deionized water of 160g and the triethylamine of 6.5g are added in afterwards, react 25min, the reaction time is preferably 120min, is obtained
To aqueous polyurethane emulsion.
The aqueous polyurethane that embodiment 5 obtains is labeled as WPU-5, and the performance test results are as shown in Tables 1 and 2.
Embodiment 6
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 220 DEG C, adds in the different Buddhist diketone diisocyanate of 26g
Ester, the polyneopentyl glycol adipate glycol (Mn=2000) of 105g, 0.4g Irganox1010,0.08g tin dilaurate two
The dimethylolpropionic acid of butyl tin and 3.0g, melting stir 80min, obtain the first intermediate；
Step 2：First intermediate is added in the second reaction kettle, the temperature of the second reaction kettle is controlled at 65 DEG C, is added in
3- (five poly- (1- (ammonia propoxyl group) propyl) amino) propyl -1- sodium sulfonates of 0.7g, reaction time 7min are obtained among second
Body；
Step 3: adding in the 1,5-PD of 3.8g into the second intermediate, temperature is increased to 220 DEG C, reacts 18min,
Obtain third intermediate；
Step 4: obtained third intermediate is added in third dispersion reaction kettle, reaction temperature is controlled at 35 DEG C, so
The deionized water of 155g is added in afterwards and the N of 6.8g, N- dimethylethanolamines react 150min, obtain aqueous polyurethane emulsion.
The aqueous polyurethane that embodiment 6 obtains is labeled as WPU-6, and the performance test results are as shown in Tables 1 and 2.
The results of performance analysis of 1 aqueous polyurethane dispersion of table
The performance test results of 2 aqueous polyurethane dispersion dry coating of table
Claims (10)
1. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion, which is characterized in that comprise the following steps：
Step 1：Under nitrogen protection, temperature of reaction kettle is increased to 140~240 DEG C, adds in diisocyanate, polymer binary
Alcohol, antioxidant, catalyst, small molecule dihydric alcohol and hydrophilic chain extender, melting stir 15-90min, obtain the first intermediate；
Step 2：The first intermediate that step 1 obtains is put into the second reaction kettle, the temperature control of the second reaction kettle exists
60-75 DEG C, sulfonate type polyamine hydrophilic chain extender is then added in, reaction time 5-10min obtains the second intermediate；
Step 3: adding in small molecule dihydric alcohol into the second intermediate that step 2 obtains, temperature is increased to 160-240 DEG C, instead
15-30min is answered, obtains third intermediate；
Step 4: the third intermediate that step 3 obtains is added in third dispersion reaction kettle, reaction temperature control 30~
50 DEG C, deionized water and neutralizer are then added in, 30-180min is reacted, obtains sulfonic waterborne polyurethane emulsion.
2. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The diisocyanate be selected from 4,4- '-diphenylmethane diisocyanates, toluene di-isocyanate(TDI), tolylene diisocyanate,
1,5- how diisocyanate, paraphenylene diisocyanate, hexamethylene diisocyanate, different Buddhist diisocyanates, hydrogenation 4,
One or more of 4- '-diphenylmethane diisocyanates.
3. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The one kind of the polymer diatomic alcohol in polyether Glycols or polyester diol.
4. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 3, which is characterized in that
The polyether Glycols are selected from the one of PolyTHF dihydric alcohol, Polyoxypropylene diol or polyoxyethylene glycol
Kind, molecular weight 2000-5000Da, the water content of polyether Glycols is in below 300ppm.
5. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 3, which is characterized in that
The polyester diol is selected from -1,4 butyl glycol ester diol of polyadipate, polyethylene glycol adipate glycol, polyadipate third
Glycol esterdiol, polyneopentyl glycol adipate glycol, polyadipate hexylene glycol neopentyl glycol esterdiol gather own Inner esterdiols
In one kind, molecular weight ranges 2000-5000, polyester diol water content is in below 300ppm.
6. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The antioxidant is selected from model Irganox1010, Irgafos168 or Irganox 1076 of BASF AG's production
In one kind.
7. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The hydrophilic chain extender is one kind in dihydromethyl propionic acid or dimethylolpropionic acid.
8. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The sulfonate type polyamine hydrophilic chain extender is 2- [(2- amino-ethyls) amino] b sodium salt, 2,4- diaminobenzene sulphurs
Sour sodium or 3- (five poly- (1- (ammonia propoxyl group) propyl) amino) propyl -1- sodium sulfonates.
9. a kind of non-solvent preparation of sulfonic waterborne polyurethane emulsion according to claim 1, which is characterized in that
The diisocyanate, polymer diatomic alcohol, antioxidant, catalyst, small molecule dihydric alcohol, hydrophilic chain extender, sulfonate type
The weight ratio of polyamine hydrophilic chain extender, deionized water and neutralizer is (20-30)：(80-120)：(0.3-0.5)：(0.05-
0.1)：(2.5-4.2)：(2.8-4.5)：(0.4-1.2)：(110-170)：(4.5-7.2).
10. the sulfonic waterborne polyurethane emulsion that the preparation method according to claim 1-9 any one obtains.
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| CN111040710A (en) * | 2019-09-29 | 2020-04-21 | 文成县鸿丰实业有限公司 | Carboxylic acid/sulfonic acid composite waterborne polyurethane adhesive and preparation method thereof |
| CN115403735A (en) * | 2022-10-13 | 2022-11-29 | 西安交通大学 | Sulfonic acid type waterborne polyurethane emulsion and preparation method thereof |
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| CN107446105A (en) * | 2017-07-28 | 2017-12-08 | 高鼎精细化工(昆山)有限公司 | A kind of sulfonic waterborne polyurethane emulsion, its product and preparation method thereof |
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| CN115403735A (en) * | 2022-10-13 | 2022-11-29 | 西安交通大学 | Sulfonic acid type waterborne polyurethane emulsion and preparation method thereof |
| CN115403735B (en) * | 2022-10-13 | 2024-01-26 | 西安交通大学 | Sulfonic acid type aqueous polyurethane emulsion and preparation method thereof |
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Application publication date: 20180619 |