CN107090069A - A kind of aqueous polyurethane preparation method of secondary rear chain extension and its dispersion liquid of preparation - Google Patents
A kind of aqueous polyurethane preparation method of secondary rear chain extension and its dispersion liquid of preparation Download PDFInfo
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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
- C08G18/08—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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- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/65—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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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Abstract
The invention discloses a kind of aqueous polyurethane preparation method of secondary rear chain extension and its obtained dispersion liquid.The rear chain extending reaction of current water soluble diamines is only confined in the water-wetted surface of polyurethane latex grain, the isocyanate groups inside oleophylic to remaining in polyurethane latex grain have no effective chain extension effect, it is difficult to fully improve the relative molecular mass of aqueous polyurethane.The method of the present invention includes polymer polyatomic alcohol and reacted under catalyst action with diisocyanate, hydrophilic chain extender, small molecule chain extender, and obtain performed polymer with solvent adjustment viscosity, nertralizer is added to neutralize, through water-soluble rear chain extender chain extension, again through oil-soluble rear chain extender it is secondary after chain extension, removed under reduced pressure solvent, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.The isocyanate groups that secondary rear chain extension method used in the present invention remains polyurethane fully react with rear chain extender, fast and effeciently improve the relative molecular mass of aqueous polyurethane.
Description
Technical field
The present invention relates to polyurethane preparation method field, more specifically a kind of aqueous polyurethane system of secondary rear chain extension
Preparation Method and its dispersion liquid of preparation.
Background technology
As people are to quality of life and the raising of environmental protection requirement, various environmental regulations are to volatile organic compound
Discharge capacity, the content of toxic solvent of thing (VOC) have strict limitation.Aqueous polyurethane is, using water as decentralized medium, to be free of
Or only contain a small amount of organic solvent water-dispersed polymer, with it is nontoxic, nonflammable, free from environmental pollution, energy-conservation, safety can
By the advantages of.As the replacer of solvent borne polyurethane material, water-base polyurethane material both has good combination property, has again
Have the advantages that not pollute, transportation safety and working environment it is good, meet environmental requirement, be that the class developed rapidly in recent years is aqueous
Material.But corresponding solvent borne polyurethane product compares, aqueous polyurethane product also has its inevitable shortcoming, such as mechanics
Intensity, water-fast solvent resistance are poor etc., and particularly to can not show a candle to solvent borne polyurethane product high for aqueous polyurethane product molecular weight.Water
The property not high essential reason of polyurethane products molecular weight is limited by aqueous polyurethane preparation method.
The preparation on high-molecular aqueous polyurethane is mainly using control base polyurethane prepolymer for use as R value (isocyanic acids at present
The molar ratio of ester and hydroxyl) or water-soluble amine to chain extension technique after aqueous polyurethane dispersing liquid.Wen Yanjia etc., which is reported, to be passed through
Change a series of base polyurethane prepolymer for use as that different formulations are made in the R values in polymerization process, with the reduction of R values, polyurethane prepolymer
The increase of body molecular mass, that is, HMW polyurethane (printing and dyeing assistant in March, 2015 the 3rd phase height of volume 32 can be prepared by dropping low r-value
The preparation of solid content aqueous polyurethane emulsion and its performance study Preparation and performance of high
solid content waterborne polyurethane emulsion.TEXTILE
AUXILIARIES.Vol.32No.3Mar.2015)。
Base polyurethane prepolymer for use as molecular weight is easily caused performed polymer viscosity greatly when larger, be difficult to disperse in emulsion process, and breast
Viscosity is big after change, is unfavorable for being made stable large arch dam aqueous polyurethane dispersing liquid.Patent applicant once reported：Pass through control
Chain extension after different water soluble diamines are carried out to aqueous polyurethane dispersing liquid, chain extending reaction after water soluble diamines are participated in, not only
The molecular weight of polyurethane, and generation urea bond are improved, urea bond polarity is strong, the mechanical property of aqueous polyurethane can be effectively improved and water-fast
Solvent resistance (influence polyurethane industrial of the different Diamines rear chain extenders to Property of Waterborne Polyurethane
.2014.Vol.29No.3).But, the rear chain extending reaction of water soluble diamines is only confined in the hydrophilic table of polyurethane latex grain
Face, the isocyanate groups inside oleophylic to remaining in polyurethane latex grain have no effective chain extension and acted on, it is difficult to fully carry
The relative molecular mass of high aqueous polyurethane.
The content of the invention
The purpose of the present invention passes through to provide a kind of preparation method of the aqueous polyurethane dispersing liquid of secondary rear chain extension
Chain extension after water-soluble diamines, then through oil-soluble diamines after secondary chain extension prepare the aqueous polyurethane dispersing liquid of HMW, with
Polyurethane relative molecular mass is significantly improved, its hypotoxicity, environmental protection, stability is good, thermodynamic property is excellent and solid content is high.
Therefore, the technical solution adopted by the present invention is：A kind of preparation side of the aqueous polyurethane dispersing liquid of secondary rear chain extension
Method, it is comprised the following steps：
Step 1), by the one or more in relative molecular mass 500-4000 polymer diatomic alcohols or polymer polyatomic alcohol
It is warming up to 100-130 DEG C, vacuum dehydration 1-2 hours；
Step 2), it is cooled to 60-80 DEG C of addition diisocyanate, nitrogen protection lower reaction 0.5-1 hours；
Step 3), appropriate catalyst is added, is reacted 1-3 hours at 60-90 DEG C, obtains the reactant of clear；
Step 4), hydrophilic chain extender, small molecule chain extender are added to step 3) reactant in, use step 3) it is anti-
Thing 0.1-30wt% solvent adjustment reaction system viscosity is answered, is reacted 1-3 hour at 60-90 DEG C, obtains clarifying sticky pre-
Aggressiveness；
Step 5), the nertralizer for being cooled to the 40-70 DEG C of tertiary amine added selected from C2-C4 or three-level hydramine is neutralized, adjustment
The pH value of performed polymer is in 6-8；
Step 6), performed polymer is scattered in deionized water under 800-2000 revs/min of high-speed stirred, addition is selected from
Chain extending reaction 0.5-2 hours after under the water-soluble rear chain extender of one-level or two grades of C2-C4 diamines, high-speed stirred, wherein water-soluble
Property rear chain extender active function groups and performed polymer in NCO mol ratios be 0.01-0.8：1；
Step 7), it is 0.02-1 to add active function groups with NCO mol ratios in performed polymer：1 is selected from C1-C3 alkyl toluene bases
Secondary rear chain extending reaction 0.5-2 under the oil-soluble rear chain extender of diamines or C1-C3 hetero atom alkyl toluene base diamines, high-speed stirred
Hour；40-70 DEG C of removal of solvent under reduced pressure, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension；
Wherein, polymer diatomic alcohol or polymer polyatomic alcohol：Hydrophilic chain extender：The mol ratio of small molecule chain extender is 1:
0.1-1:0.1-1, and polymer diatomic alcohol, polymer polyatomic alcohol, the total mole number of hydrophilic chain extender and small molecule chain extender with
The mole ratio of diisocyanate is 1:2-1.
Preferably, step 1) polymer diatomic alcohol or polymer polyatomic alcohol be PEPA and PPG one
Plant or a variety of mixing.
Preferably, step 2) diisocyanate be toluene di-isocyanate(TDI), IPDI, six methylenes
Group diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, to benzene two
One or more mixing in isocyanates, XDI.
Preferably, step 3) catalyst be one or more mixing in dibutyl tin laurate, stannous octoate.
Preferably, step 4) hydrophilic chain extender be 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids, ethylenediamine
One or more mixing in base ethyl sulfonic acid sodium, second dihydroxy ethyl sulfonic acid sodium.
Be used as preferred, step 4) small molecule chain extender for ethylene glycol, 1,4- butanediols, 3- methyl pentanediols, one contracting two
Ethylene glycol, 2- methyl propanediols, neopentyl glycol, 1,6-HD, trimethylolpropane, propane diols, one kind in ethylene glycol or
A variety of mixing.
Preferably, step 4) solvent be acetone, butanone, DMF, 1-METHYLPYRROLIDONE in
One or more mixing.
Preferably, step 5) nertralizer be triethylamine, triethanolamine, diethanol amine, tri-n-butylamine, sodium hydroxide in
One or more mixing.
Preferably, step 6) water-soluble rear chain extender be ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine, hexamethylene two
One or more mixing in amine, N, N- dimethyl-ethylenediamines, IPD, piperazine.
Preferably, step 7) oil-soluble rear chain extender be 2- methyl-pentamethylenediamines, 3,5- diethyl toluene diamines, 3,
The double Zhong Ding aminobenzenes of the chloro- 4,4'- diphenylmethanediamiands of 5- dimethythiotoluene diamines, 3,3'- bis-, 1,4-, the double Zhong Ding of 4,4'-
Aminodiphenylmethane, N, the double sec-amyl cyclohexane diamine one or more mixing of N'-.
Preferably, step 3) catalyst and step 2) isocyanates mol ratio be 0.0001-0.001.
Preferably, step 6) water-soluble rear chain extender active function groups and performed polymer in NCO mol ratios be 0.1-
0.7：1.
Preferably, step 7) to add NCO mol ratios in active function groups and performed polymer be 0.1-0.8：1.
The aqueous polyurethane dispersing liquid of the secondary rear chain extension obtained it is a further object of the present invention to provide above-mentioned preparation method.
Under water dispersity, waterborne polyurethane resin mutually assembles granular into latex because of hydrophobic segment part, containing from
Subchain section and hydrophilic segment are largely distributed in emulsion particle surface, because emulsion particle surface is prevented between particle with like charges
Self aggregation, and then form stable surface hydrophilic and the emulsion particle of internal oleophylic.The rear chain extending reaction of water soluble diamines
It is only confined in the water-wetted surface of polyurethane latex grain, it is difficult to inside the oleophylic for entering polyurethane latex grain, thus to remaining in
Isocyanate groups inside the oleophylic of polyurethane latex grain have no effective chain extension effect.Oil-soluble rear chain extender is easily entered
Inside the oleophylic of polyurethane latex grain, therefore, after water soluble diamines on the basis of chain extension, it can be added by suitable mode
Oil-soluble rear chain extender carries out secondary rear chain extension to the isocyanate groups inside aqueous polyurethane emulsion particle oleophylic, quickly to fill
Divide the relative molecular mass for improving aqueous polyurethane.
With the addition of water-soluble rear chain extender, the increase of polyurethane molecular amount is average to the hydrophilic group on each strand
Group increases, the hydrophily enhancing of strand, and then forms stable polyurethane dispersing liquid.Add the entrance of oil-soluble rear chain extender
Polyurethane latex grain oleophylic inside, to remain in polyurethane latex grain oleophylic inside isocyanate groups carry out chain extension with
Obtain HMW polyurethane.In moisture dephasing, the reaction rate of water-soluble rear chain extender and isocyanates is much larger than oil-soluble
The reaction rate of rear chain extender and isocyanates.If first adding oil-soluble rear chain extender, then it can not efficiently accomplish after the first step
Chain extension, it is impossible to form stable polyurethane dispersing liquid, identical effect is also unable to reach even if water-soluble rear chain extender is added.
The preparation method of the present invention provides water-soluble diamines chain extension behind the surface of polyurethane particles, adds oil-soluble two
The isocyanates of the part residual of inside of the amine with being wrapped in polyurethane particles reacts, and carries out secondary rear chain extension, quick effective
Ground improves the relative molecular mass of aqueous polyurethane, increases substantially the tensile strength and extension at break of aqueous polyurethane film
Rate.Secondary chain extension does not form crosslinking, does not change dispersion particle diameters, thus does not influence the stability of dispersion.Using simple mixed
Technique is closed, normal temperature chain extension is this inexpensive, simple to operate, and the method that can significantly lift Properties of Aqueous Polyurethane
With larger commercial application value.
Embodiment
Following examples further illustrate technical scheme, but not as limiting the scope of the invention.
Embodiment 1
By the PCDL of 100g (0.05 mole) relative molecular mass 2000,110g (0.11 mole) average molecular
Polypropylene oxide glycol, the polypropylene oxide glycol of 5g (0.0017 mole) relative molecular mass 3000 and the 100g of quality 1000
The polytetrahydrofuran diol of (0.1 mole) relative molecular mass 1000 is at 120 DEG C, vacuum dehydration 1.5h.It is cooled to 65 DEG C, plus
Enter 159.5g (0.718 mole) IPDI, nitrogen protection reacts 1h at 80 DEG C.Add 0.1g stannous octoates
(0.000247 mole), 1.5h is reacted at 80 DEG C.12g (0.081 mole) 2,2- dimethylolpropionic acids are added, (0.057 rubs 6g
You) diglycol, 60g butanone reacts 3h at 80 DEG C, obtains clarifying sticky performed polymer.50 DEG C are cooled to, 9.0g is added
Triethylamine is neutralized, and performed polymer is scattered in 1134g deionized waters under 1000r/min high-speed stirred, adds 8.6g
Chain extension after (0.143 mole) ethylenediamine, high-speed stirred 0.5h adds the secondary rear expansion of 16g (0.138 mole) 2- methyl-pentamethylenediamines
Chain, high-speed stirred 1h, removal of solvent under reduced pressure obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
Embodiment 2
By the poly adipate succinic acid ester of 100g (0.2 mole) relative molecular mass 500 at 120 DEG C, vacuum dehydration 1h.
60 DEG C are cooled to, 72g (0.414 mole) toluene di-isocyanate(TDI) is added, nitrogen protection reacts 1h at 80 DEG C.Add 0.03g
(0.0000475 mole) dibutyl tin laurate, 1.5h is reacted at 80 DEG C.Add 4g (0.03 mole) 2,2- dihydroxymethyls
Propionic acid, 3g (0.03 mole) neopentyl glycol, 5g 1-METHYLPYRROLIDONEs, 25g butanone reacts 3h at 80 DEG C, obtains clarification sticky
Performed polymer.50 DEG C are cooled to, 3.6g triethylamines is added and neutralizes, be scattered in performed polymer under 1000r/min high-speed stirred
In 104g deionized waters, chain extension after 3.9g (0.045 mole) piperazine is added, high-speed stirred 0.5h adds 5g (0.028 mole) 3,
The secondary rear chain extension of 5- diethyl toluene diamines, high-speed stirred 1h, removal of solvent under reduced pressure obtains the aqueous polyurethane of secondary rear chain extension
Dispersion liquid.
Embodiment 3
By the polypropylene oxide glycol of 200g (0.1 mole) relative molecular mass 2000 at 120 DEG C, vacuum dehydration
1.5h.65 DEG C are cooled to, 76.4g (0.344 mole) IPDI is added, nitrogen protection is reacted at 80 DEG C
1h.0.06g (0.000148 mole) stannous octoate is added, 1.5h is reacted at 80 DEG C.Add 8g (0.06 mole) 2,2- dihydroxies
Methylpropanoic acid, 5g (0.06 mole) BDO, 10g 1-METHYLPYRROLIDONEs, 40g butanone reacts 3h at 80 DEG C, obtained
The sticky performed polymer of clarification.50 DEG C are cooled to, 7.2g triethylamines is added and neutralizes, by pre-polymerization under 1000r/min high-speed stirred
Body is scattered in 245g deionized waters, adds chain extension after 3.0g (0.05 mole) ethylenediamine, and high-speed stirred 0.5h adds 5.2g
The secondary rear chain extension of (0.029 mole) 3,5- diethyl toluene diamines, high-speed stirred 1h, removal of solvent under reduced pressure obtains secondary rear expansion
The aqueous polyurethane dispersing liquid of chain.
Embodiment 4
By the polytetrahydrofuran diol of 200g (0.067 mole) relative molecular mass 3000 at 120 DEG C, vacuum dehydration
1.5h.65 DEG C are cooled to, 70g (0.28 mole) methyl diphenylene diisocyanate is added, nitrogen protection reacts 1h at 80 DEG C.
0.06g (0.000148 mole) stannous octoate is added, 1.5h is reacted at 80 DEG C.Add 9g (0.061 mole) 2,2- dihydroxy first
Base butyric acid, 5g (0.05 mole) diglycol, 40g butanone reacts 3h at 80 DEG C, obtains clarifying sticky performed polymer.Drop
Temperature adds 10.8g triethanolamines and neutralized to 50 DEG C, under 1000r/min high-speed stirred by performed polymer be scattered in 250g go from
In sub- water, chain extension after 2.6g (0.03 mole) piperazine is added, high-speed stirred 0.5h adds 5.6g (0.026 mole) 3,5- diformazans
The secondary rear chain extension of sulfenyl toluenediamine, high-speed stirred 1h, removal of solvent under reduced pressure, the aqueous polyurethane for obtaining secondary rear chain extension disperses
Liquid.
Embodiment 5
By the poly adipate succinic acid ester of 100g (0.1 mole) relative molecular mass 1000 and 200g (0.067 mole) phase
To the polytetrahydrofuran diol of molecular mass 3000 at 120 DEG C, vacuum dehydration 1.5h.65 DEG C are cooled to, 97.6g is added
(0.44 mole) IPDI and 18.5g (0.11 mole) hexamethylene diisocyanate, nitrogen are protected 80
1h is reacted at DEG C.0.1g (0.000247 mole) stannous octoate is added, 1.5h is reacted at 80 DEG C.Add 12g (0.09 mole)
2,2- dihydromethyl propionic acids, 8g (0.08 mole) neopentyl glycol, 40g butanone reacts 3h at 80 DEG C, obtains clarifying sticky pre-polymerization
Body.50 DEG C are cooled to, 11.7g triethylamines is added and neutralizes, performed polymer is scattered in 480g under 1000r/min high-speed stirred
In ionized water, chain extension after 5.5g (0.092 mole) ethylenediamine is added, high-speed stirred 0.5h adds 15g (0.084 mole) 3,5-
The secondary rear chain extension of diethyl toluene diamine, high-speed stirred 1h, removal of solvent under reduced pressure obtains the aqueous polyurethane point of secondary rear chain extension
Dispersion liquid.
Embodiment 6
By the polyethylene glycol of 300g (0.15 mole) relative molecular mass 2000 at 120 DEG C, vacuum dehydration 1.5h.Cooling
To 65 DEG C, 84.3g (0.38 mole) IPDI is added, nitrogen protection reacts 1h at 80 DEG C.Add 0.1g
(0.000247 mole) stannous octoate, 1.5h is reacted at 80 DEG C.Add 12g (0.081 mole) 2,2- dimethylolpropionic acids, 2g
(0.015 mole) trimethylolpropane, 100g acetone reacts 4h at 65 DEG C, obtains clarifying sticky performed polymer.It is cooled to 50
DEG C, add 15.7g triethanolamines and neutralize, performed polymer is scattered in 453g deionized waters under 1000r/min high-speed stirred,
Chain extension after 5.3g (0.062 mole) piperazine is added, high-speed stirred 0.5h adds 15g (0.084 mole) 3,5- diethyltoluenes two
The secondary rear chain extension of amine, high-speed stirred 1h, removal of solvent under reduced pressure obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
Embodiment 7
By the makrolon of 300g (0.1 mole) relative molecular mass 3000 at 120 DEG C, vacuum dehydration 1.5h.Cooling
To 65 DEG C, 66.3g (0.381 mole) toluene di-isocyanate(TDI) is added, nitrogen protection reacts 1h at 80 DEG C.Add 0.1g
(0.000247 mole) stannous octoate, 1.5h is reacted at 80 DEG C.Add 12g (0.09 mole) 2,2- dihydromethyl propionic acids, 4g
(0.064 mole) ethylene glycol, 100g acetone reacts 4h at 65 DEG C, obtains clarifying sticky performed polymer.It is cooled to 50 DEG C, addition
12.7g triethylamines are neutralized, and performed polymer is scattered in 364g deionized waters under 1000r/min high-speed stirred, add 3.8g
Chain extension after (0.063 mole) ethylenediamine, high-speed stirred 0.5h adds 12g (0.067 mole) 3,5- diethyl toluene diamines secondary
Chain extension, high-speed stirred 1h, removal of solvent under reduced pressure, obtain the aqueous polyurethane dispersing liquid of secondary rear chain extension afterwards.
Embodiment 8
By the polyadipate hexylene glycol ester of 100g (0.033 mole) relative molecular mass 3000,100g (0.05 mole) phase
To the polypropylene oxide glycol of molecular mass 2000, the polytetrahydrofuran diol of 100g (0.05 mole) relative molecular mass 2000
At 120 DEG C, vacuum dehydration 2h.65 DEG C are cooled to, 27.3g (0.157 mole) toluene di-isocyanate(TDI), 52.2g is added
(0.235 mole) IPDI, nitrogen protection reacts 1h at 80 DEG C.Add 0.1g (0.000247 mole) pungent
Sour stannous, 1.5h is reacted at 80 DEG C.Add 12g (0.09 mole) 2,2- dihydromethyl propionic acids, 4g (0.04 mole) new penta 2
Alcohol, 200g acetone reacts 4h at 65 DEG C, obtains clarifying sticky performed polymer.50 DEG C are cooled to, 11.7g triethylamines is added and neutralizes,
Performed polymer is scattered in 263g deionized waters under 1000r/min high-speed stirred, 3.8g (0.063 mole) ethylenediamine is added
Chain extension, high-speed stirred 0.5h, add the secondary rear chain extension of 12g (0.067 mole) 3,5- diethyl toluene diamines, high-speed stirred afterwards
1h, removal of solvent under reduced pressure obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
Experimental result is tested and analyzed：
Experimental test procedures
1. emulsion film ATR infrared tests：Using Fourier infrared spectrograph.
2. emulsion film membrance casting condition：After emulsion nature film forming is dried, 60 DEG C of drying 2h, the glued membrane after drying does following survey
Take temperature and levy；
3. water-fast solvent resistance test：
Glued membrane is cut into 30mm × 30mm sizes.Immersed at 25 DEG C in deionized water, ethanol and weigh it before immersion after 24h
Mass change afterwards.
The computational methods of rate of body weight gain are as follows：
Rate of body weight gain=(m2-m1)/m1 × 100%
Wherein, m1 and m2 are respectively the quality of sample before and after immersion.
Analysis of experimental results：
By taking embodiment 1 as an example, Tables 1 and 2 is listed on the basis of 45% water-soluble amine chain extension ratio respectively, uses oil
Dissolubility diamines carry out secondary chain extension different proportion parameter and corresponding film forming matter it is water-fast/solvent resistance.
The oil-soluble diamines of table 1 carries out the different proportion design of secondary chain extension
The oil-soluble diamines of table 2 difference chain extension ratio is water-fast to film forming matter/influence of solvent resistance
| Sample number into spectrum | Water/% | Ethanol/% | Butanone/% |
| WPU-1 | 11.2 | 104.7 | 255.6 |
| WPU-2 | 9.7 | 100.3 | 251.4 |
| WPU-3 | 7.3 | 98.6 | 246.8 |
| WPU-4 | 5.2 | 97.3 | 230.1 |
| WPU-5 | 5.4 | 96.5 | 234.2 |
It can be seen from Tables 1 and 2 when oil-soluble diamines chain extension ratio is 30% or so, emulsion film forming thing
Water-fast/solvent resistance is crossed to optimum value, and substantially more excellent than the simple film forming physical performance with water-soluble diamines chain extension, this
Illustrate the obvious effect that the secondary chain extension of oil-soluble diamines is played really.
Likewise, in order to further prove oil-soluble diamines chain extension effect, for different oil-soluble diamines chain extension ratios
Carbonyl absorption peak in emulsion infrared spectrum carries out peak-fit processing, then calculates respectively and obtains carbamic acid ester carbonyl group and urea groups carbonyl
The relative absorbance peak area accounting data of base, as a result as shown in table 3.
The infrared absorption peak area of the different oil-soluble diamines chain extension ratio emulsion carbamic acid ester carbonyl groups of table 3 and ureidocarbonyl
Accounting
Influence of the different oil-soluble diamines chain extension ratios of table 4 to polymer molecular weight
As can be seen from Table 3, when oil-soluble amine, which expands ratio, increases to 30% from 0%, with carbamate groups carbonyl
Base is internal standard compound, and the relative amount of urea groups is stepped up, and illustrates the significant degree of amine chain extension on the basis of water-soluble amine chain extension,
Further increase.This substantially verifies that oil-soluble diamines is effectively diffused into inside polyurethane latex grain oleophylic and generation two really
Secondary chain extending reaction.Polymer molecular weight variation tendency is similarly proved under the different oil-soluble amine chain extension ratio situations that table 4 is listed
This viewpoint.
Claims (10)
1. a kind of preparation method of the aqueous polyurethane dispersing liquid of secondary rear chain extension, it is comprised the following steps：
Step 1), the one or more in relative molecular mass 500-4000 polymer diatomic alcohols or polymer polyatomic alcohol are heated up
To 100-130 DEG C, vacuum dehydration 1-2 hours；
Step 2), it is cooled to 60-80 DEG C of addition diisocyanate, nitrogen protection lower reaction 0.5-1 hours；
Step 3), appropriate catalyst is added, is reacted 1-3 hours at 60-90 DEG C, obtains the reactant of clear；
Step 4), hydrophilic chain extender, small molecule chain extender are added to step 3) reactant in, use step 3) reactant
0.1-30wt% solvent adjustment reaction system viscosity, reacts 1-3 hours at 60-90 DEG C, obtains clarifying sticky performed polymer；
Step 5), the 40-70 DEG C of nertralizer added selected from C2-C4 tertiary amines or three-level hydramine neutralization is cooled to, performed polymer is adjusted
PH value in 6-8；
Step 6), performed polymer is scattered in deionized water under 800-2000 revs/min of high-speed stirred, adds and is selected from one-level
Or the water-soluble rear chain extender of two grades of C2-C4 diamines, under high-speed stirred after chain extending reaction 0.5-2 hour, wherein after water solubility
Chain extender active function groups are 0.01-0.8 with NCO mol ratios in performed polymer：1；
Step 7), it is 0.02-1 to add active function groups with NCO mol ratios in performed polymer：1 is selected from C1-C3 alkyl toluene base diamines
Or the oil-soluble rear chain extender of C1-C3 hetero atom alkyl toluene base diamines, secondary rear chain extending reaction 0.5-2 is small under high-speed stirred
When；40-70 DEG C of removal of solvent under reduced pressure, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension；
Wherein, polymer diatomic alcohol or polymer polyatomic alcohol：Hydrophilic chain extender：The mol ratio of small molecule chain extender is 1:0.1-1:
0.1-1, and polymer diatomic alcohol, polymer polyatomic alcohol, the total mole number and two isocyanides of hydrophilic chain extender and small molecule chain extender
The mole ratio of acid esters is 1:2-1.
2. preparation method according to claim 1, it is characterised in that described diisocyanate is toluene diisocynate
Ester, IPDI, hexamethylene diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride two
One or more mixing in isocyanates, naphthalene diisocyanate, PPDI, XDI.
3. preparation method according to claim 1, it is characterised in that described catalyst be dibutyl tin laurate,
One or more mixing in stannous octoate.
4. preparation method according to claim 1, it is characterised in that described hydrophilic chain extender is 2,2- dihydroxymethyls third
One or more mixing in acid, 2,2- dimethylolpropionic acids, ethylenediamine base ethyl sulfonic acid sodium, second dihydroxy ethyl sulfonic acid sodium.
5. preparation method according to claim 1, it is characterised in that described small molecule chain extender be ethylene glycol, Isosorbide-5-Nitrae-
Butanediol, 3- methyl pentanediols, diglycol, 2- methyl propanediols, neopentyl glycol, 1,6-HD, trihydroxy methyl third
One or more mixing in alkane, propane diols, ethylene glycol.
6. preparation method according to claim 1, it is characterised in that described solvent is acetone, butanone, N, N- dimethyl
One or more mixing in formamide, 1-METHYLPYRROLIDONE.
7. preparation method according to claim 1, it is characterised in that described nertralizer is triethylamine, triethanolamine, two
One or more mixing in monoethanolamine, tri-n-butylamine, sodium hydroxide.
8. preparation method according to claim 1, it is characterised in that described water-soluble rear chain extender is ethylenediamine, fourth
One or more in diamines, pentanediamine, hexamethylene diamine, cyclohexanediamine, N, N- dimethyl-ethylenediamines, IPD, piperazine
Mixing.
9. preparation method according to claim 1, it is characterised in that described oil-soluble rear chain extender is 2- methyl-penta
The chloro- 4,4'- diphenylmethanediamiands of diamines, 3,5- diethyl toluene diamines, 3,5- dimethythiotoluene diamines, 3,3'- bis-, 1,
The double Zhong Ding aminobenzenes of 4-, the double Zhong Ding aminodiphenylmethanes of 4,4'-, N, the double sec-amyl cyclohexane diamine one or more of N'- are mixed
Close.
10. a kind of aqueous polyurethane dispersing liquid prepared according to any one of claim 1-9 preparation method.
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