CN107090069B - A kind of secondary the aqueous polyurethane preparation method of chain extension and its dispersion liquid of preparation afterwards - Google Patents
A kind of secondary the aqueous polyurethane preparation method of chain extension and its dispersion liquid of preparation afterwards 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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- 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
- C08G18/6625—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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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Abstract
The invention discloses a kind of aqueous polyurethane preparation method of secondary rear chain extension and its dispersion liquids obtained.The rear chain extending reaction of current water soluble diamines is only confined in the water-wetted surface of polyurethane latex grain, effective chain extension effect is had no to the isocyanate groups inside the oleophylic for remaining in polyurethane latex grain, it is difficult to sufficiently improve the relative molecular mass of aqueous polyurethane.The method of the present invention includes polymer polyatomic alcohols to react under the action of catalyst with diisocyanate, hydrophilic chain extender, small molecule chain extender, and performed polymer is obtained with solvent adjustment viscosity, neutralizer is added to neutralize, through water-soluble rear chain extender chain extension, the chain extension after oil-soluble rear chain extender is secondary again, removed under reduced pressure solvent obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.Secondary rear chain extension method used in the present invention reacts the remaining isocyanate groups of polyurethane sufficiently with rear chain extender, fast and effeciently improves 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 technique
Raising with people to quality of life and environmental protection requirement, various environmental regulations are to volatile organic compound
Discharge amount, the content of toxic solvent of object (VOC) have stringent limitation.Aqueous polyurethane is free of using water as decentralized medium
Or the water-dispersed polymer of a small amount of organic solvent is contained only, have nontoxic, nonflammable, free from environmental pollution, energy saving, safety can
By the advantages that.As the replacer of solvent borne polyurethane material, water-base polyurethane material had not only had good comprehensive performance, but also tool
Have the advantages that not pollute, transportation safety and working environment it is good, meet environmental requirement, be that one kind for rapidly developing in recent years is aqueous
Material.But corresponding solvent borne polyurethane product compares, and aqueous polyurethane product also has the shortcomings that its is inevitable, such as mechanics
Intensity, water-fast solvent resistance are poor etc., and especially it is high to can not show a candle to solvent borne polyurethane product 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.
At present about the preparation of high-molecular aqueous polyurethane mainly using control base polyurethane prepolymer for use as R value (isocyanic acid
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 value in polymerization process, with the reduction of R value, polyurethane prepolymer
Body molecular mass increases, i.e., drop low r-value can prepare high molecular weight polyurethane (printing and dyeing assistant in March, 2015 the 3rd phase height of volume 32
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 easily leads to performed polymer large viscosity when larger, be not easy to disperse in emulsion process, and cream
Viscosity is big after change, is unfavorable for being made stable large arch dam aqueous polyurethane dispersing liquid.Patent applicant once reported: passing through control
Chain extension after different water soluble diamines carry out aqueous polyurethane dispersing liquid, chain extending reaction after water soluble diamines participate in, not only
The molecular weight of polyurethane is improved, and generates urea bond, urea bond polarity is strong, can effectively improve the mechanical property of aqueous polyurethane 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 has no effective chain extension to the isocyanate groups inside the oleophylic for remaining in polyurethane latex grain and acts on, it is difficult to sufficiently mention
The relative molecular mass of high aqueous polyurethane.
Summary of the invention
A purpose of the invention is to provide a kind of preparation method of the aqueous polyurethane dispersing liquid of secondary rear chain extension, that is, is passed through
Chain extension after water-soluble diamines, then chain extension prepares the aqueous polyurethane dispersing liquid of high molecular weight after oil-soluble diamines is secondary, with
Polyurethane relative molecular mass is significantly improved, hypotoxicity, environmental protection, stability is good, thermodynamic property is excellent and solid content is high.
For this purpose, the technical solution adopted by the present invention are as follows: a kind of preparation side of the aqueous polyurethane dispersing liquid of secondary rear chain extension
Method, it includes following steps:
Step 1), by one of relative molecular mass 500-4000 polymer diatomic alcohol or polymer polyatomic alcohol or a variety of
It is warming up to 100-130 DEG C, vacuum dehydration 1-2 hours；
Step 2) is cooled to 60-80 DEG C of addition diisocyanate, reacts 0.5-1 hours under nitrogen protection；
Suitable catalyst is added in step 3), reacts 1-3 hours at 60-90 DEG C, obtains the reactant of clear；
Hydrophilic chain extender, small molecule chain extender are added in the reactant of step 3) by step 4), use the anti-of step 3)
The solvent adjustment reaction system viscosity for answering object 0.1-30wt% is reacted 1-3 hours at 60-90 DEG C, obtains clarifying sticky pre-
Aggressiveness；
Step 5), the neutralizer for being cooled to tertiary amine or three-level hydramine that 40-70 DEG C is added selected from C2-C4 neutralize, adjustment
The pH value of performed polymer is in 6-8；
Step 6) disperses performed polymer in deionized water under 800-2000 revs/min of high-speed stirred, and addition is selected from
The water-soluble rear chain extender of the C2-C4 diamines of level-one or second level, under high-speed stirred after chain extending reaction 0.5-2 hours, wherein water-soluble
Property rear chain extender active function groups and performed polymer in NCO molar ratio be 0.01-0.8:1；
Step 7), it is that 0.02-1:1 is selected from C1-C3 alkyl toluene base that NCO molar ratio in active function groups and performed polymer, which is added,
The oil-soluble rear chain extender of diamines or C1-C3 hetero atom alkyl toluene base diamines, it is secondary under high-speed stirred after chain extending reaction 0.5-2
Hour；40-70 DEG C is removed under reduced pressure solvent, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension；
Wherein, polymer diatomic alcohol or polymer polyatomic alcohol: hydrophilic chain extender: the molar ratio of small molecule chain extender is 1:
0.1-1:0.1-1, and polymer diatomic alcohol, polymer polyatomic alcohol, hydrophilic chain extender and small molecule chain extender total mole number with
The mole ratio of diisocyanate is 1:2-1.
Preferably, the polymer diatomic alcohol or polymer polyatomic alcohol of step 1) are the pure and mild polyether polyol one of polyester polyols
Kind or a variety of mixing.
Preferably, the diisocyanate of step 2) is toluene di-isocyanate(TDI), isophorone diisocyanate, six methylenes
Group diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, to benzene two
One of isocyanates, benzene dimethylene diisocyanate or a variety of mixing.
Preferably, the catalyst of step 3) is one of dibutyl tin dilaurate, stannous octoate or a variety of mixing.
Preferably, the hydrophilic chain extender of step 4) is 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid, ethylenediamine
One of base ethanesulfonic acid sodium, second dihydroxy ethanesulfonic acid sodium or a variety of mixing.
Preferably, the small molecule chain extender of step 4) is ethylene glycol, 1,4- butanediol, 3- methyl pentanediol, a contracting two
One of ethylene glycol, 2- methyl propanediol, neopentyl glycol, 1,6-HD, trimethylolpropane, propylene glycol, ethylene glycol or
A variety of mixing.
Preferably, the solvent of step 4) is acetone, in butanone, n,N-Dimethylformamide, N-Methyl pyrrolidone
One or more mixing.
Preferably, the neutralizer of step 5) is triethylamine, in triethanolamine, diethanol amine, tri-n-butylamine, sodium hydroxide
One or more mixing.
Preferably, the water-soluble rear chain extender of step 6) is ethylenediamine, butanediamine, pentanediamine, hexamethylene diamine, hexamethylene two
Amine, N, one of N- dimethyl-ethylenediamine, isophorone diamine, piperazine or a variety of mixing.
Preferably, the oil-soluble rear chain extender of step 7) be 2- methyl-pentamethylenediamine, 3,5- diethyl toluene diamine, 3,
5- dimethythiotoluene diamine, the chloro- 4,4'- diphenylmethanediamiand of 3,3'- bis-, the bis- Zhong Ding aminobenzenes of 1,4-, the bis- Zhong Ding of 4,4'-
Aminodiphenylmethane, N, the bis- one or more mixing of sec-amyl cyclohexane diamine of N'-.
Preferably, the isocyanates molar ratio of the catalyst of step 3) and step 2) is 0.0001-0.001.
Preferably, NCO molar ratio is 0.1- in the water-soluble rear chain extender active function groups of step 6) and performed polymer
0.7:1.
Preferably, it is 0.1-0.8:1 that NCO molar ratio in active function groups and performed polymer, which is added, in step 7).
It is a further object of the present invention to provide the aqueous polyurethane dispersing liquids for the secondary rear chain extension that above-mentioned preparation method obtains.
Under water dispersion state, waterborne polyurethane resin because hydrophobic segment part mutually assemble into latex it is granular, containing from
Subchain section and hydrophilic segment are largely distributed in emulsion particle surface, since emulsion particle surface prevents 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 into inside the oleophylic of 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 easily enters
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, polyurethane molecular amount increases, 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
Inside the oleophylic of polyurethane latex grain, to inside the oleophylic for remaining in polyurethane latex grain isocyanate groups carry out chain extension with
Obtain high molecular weight 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 oil-soluble rear chain extender is first added, then after can not efficiently accomplishing the first step
Chain extension cannot form stable polyurethane dispersing liquid, and identical effect is unable to reach adding water-soluble rear chain extender.
Preparation method of the invention provides water-soluble diamines chain extension behind the surface of polyurethane particles, adds oil-soluble two
Amine is reacted with the remaining isocyanates in the part for the inside for being wrapped in polyurethane particles, carries out secondary rear chain extension, quickly and effectively
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, because of the stability without influencing dispersion.Using simple mixed
Close technique, room temperature chain extension, this low cost, method easy to operate, and can significantly promoting Properties of Aqueous Polyurethane
With biggish commercial application value.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
Embodiment 1
By the polycarbonate glycol of 100g (0.05 mole) relative molecular mass 2000,110g (0.11 mole) average molecular
Polypropylene oxide glycol, the polypropylene oxide glycol and 100g of 5g (0.0017 mole) relative molecular mass 3000 of quality 1000
The polytetrahydrofuran diol of (0.1 mole) relative molecular mass 1000 is at 120 DEG C, vacuum dehydration 1.5h.65 DEG C are cooled to, is added
Enter 159.5g (0.718 mole) isophorone diisocyanate, nitrogen protection reacts 1h at 80 DEG C.0.1g stannous octoate is added
(0.000247 mole), reacts 1.5h at 80 DEG C.12g (0.081 mole) 2,2- dimethylolpropionic acid is 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 neutralizes, and disperses performed polymer in 1134g deionized water under the high-speed stirred of 1000r/min, and 8.6g is added
The secondary rear expansion of 16g (0.138 mole) 2- methyl-pentamethylenediamine is added in chain extension after (0.143 mole) ethylenediamine, high-speed stirred 0.5h
Chain, high-speed stirred 1h, is removed under reduced pressure solvent, 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.0.03g is added
(0.0000475 mole) dibutyl tin dilaurate, reacts 1.5h at 80 DEG C.4g (0.03 mole) 2,2- dihydroxymethyl is added
Propionic acid, 3g (0.03 mole) neopentyl glycol, 5g N-Methyl pyrrolidone, 25g butanone react 3h at 80 DEG C, obtain clarifying sticky
Performed polymer.50 DEG C are cooled to, 3.6g triethylamine is added and neutralizes, disperses performed polymer under the high-speed stirred of 1000r/min
In 104g deionized water, chain extension after 3.9g (0.045 mole) piperazine is added, 5g (0.028 mole) 3 is added in high-speed stirred 0.5h,
Solvent is removed under reduced pressure in chain extension after 5- diethyl toluene diamine is secondary, high-speed stirred 1h, 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) isophorone diisocyanate is added, nitrogen protection is reacted at 80 DEG C
1h.0.06g (0.000148 mole) stannous octoate is added, reacts 1.5h at 80 DEG C.8g (0.06 mole) 2,2- dihydroxy is added
Methylpropanoic acid, 5g (0.06 mole) 1,4-butanediol, 10g N-Methyl pyrrolidone, 40g butanone react 3h at 80 DEG C, obtain
Clarify sticky performed polymer.50 DEG C are cooled to, 7.2g triethylamine is added and neutralizes, by pre-polymerization under the high-speed stirred of 1000r/min
Body is scattered in 245g deionized water, and chain extension after 3.0g (0.05 mole) ethylenediamine is added, and 5.2g is added in high-speed stirred 0.5h
Solvent is removed under reduced pressure in chain extension after (0.029 mole) 3,5- diethyl toluene diamine is secondary, high-speed stirred 1h, 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, reacts 1.5h at 80 DEG C.9g (0.061 mole) 2,2- dihydroxy first is added
Base butyric acid, 5g (0.05 mole) diglycol, 40g butanone react 3h at 80 DEG C, obtain clarifying sticky performed polymer.Drop
Temperature to 50 DEG C, be added 10.8g triethanolamine neutralize, under the high-speed stirred of 1000r/min by performed polymer be scattered in 250g go from
In sub- water, chain extension after 2.6g (0.03 mole) piperazine is added, 5.6g (0.026 mole) 3,5- diformazan is added in high-speed stirred 0.5h
Solvent is removed under reduced pressure in chain extension after sulfenyl toluenediamine is secondary, high-speed stirred 1h, obtains the aqueous polyurethane dispersion of secondary rear chain extension
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) isophorone diisocyanate and 18.5g (0.11 mole) hexamethylene diisocyanate, nitrogen protection is 80
1h is reacted at DEG C.0.1g (0.000247 mole) stannous octoate is added, reacts 1.5h at 80 DEG C.It is added 12g (0.09 mole)
2,2- dihydromethyl propionic acids, 8g (0.08 mole) neopentyl glycol, 40g butanone react 3h at 80 DEG C, obtain clarifying sticky pre-polymerization
Body.50 DEG C are cooled to, 11.7g triethylamine is added and neutralizes, disperses 480g for performed polymer under the high-speed stirred of 1000r/min
In ionized water, chain extension after 5.5g (0.092 mole) ethylenediamine is added, 15g (0.084 mole) 3,5- is added in high-speed stirred 0.5h
Solvent is removed under reduced pressure in chain extension after diethyl toluene diamine is secondary, high-speed stirred 1h, 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) isophorone diisocyanate is added, nitrogen protection reacts 1h at 80 DEG C.0.1g is added
(0.000247 mole) stannous octoate, reacts 1.5h at 80 DEG C.12g (0.081 mole) 2,2- dimethylolpropionic acid, 2g is added
(0.015 mole) trimethylolpropane, 100g acetone react 4h at 65 DEG C, obtain clarifying sticky performed polymer.It is cooled to 50
DEG C, 15.7g triethanolamine is added and neutralizes, disperses performed polymer in 453g deionized water under the high-speed stirred of 1000r/min,
15g (0.084 mole) 3,5- diethyltoluene two is added in chain extension after addition 5.3g (0.062 mole) piperazine, high-speed stirred 0.5h
Solvent is removed under reduced pressure in chain extension after amine is secondary, high-speed stirred 1h, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
Embodiment 7
By the polycarbonate 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.0.1g is added
(0.000247 mole) stannous octoate, reacts 1.5h at 80 DEG C.12g (0.09 mole) 2,2- dihydromethyl propionic acid, 4g is added
(0.064 mole) ethylene glycol, 100g acetone react 4h at 65 DEG C, obtain clarifying sticky performed polymer.50 DEG C are cooled to, is added
12.7g triethylamine neutralizes, and disperses performed polymer in 364g deionized water under the high-speed stirred of 1000r/min, and 3.8g is added
It is secondary that 12g (0.067 mole) 3,5- diethyl toluene diamine is added in chain extension after (0.063 mole) ethylenediamine, high-speed stirred 0.5h
Chain extension afterwards, high-speed stirred 1h, is removed under reduced pressure solvent, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
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) isophorone diisocyanate, nitrogen protection react 1h at 80 DEG C.It is pungent that 0.1g (0.000247 mole) is added
Sour stannous reacts 1.5h at 80 DEG C.12g (0.09 mole) 2,2- dihydromethyl propionic acid, 4g (0.04 mole) new penta 2 is added
Alcohol, 200g acetone react 4h at 65 DEG C, obtain clarifying sticky performed polymer.50 DEG C are cooled to, 11.7g triethylamine is added and neutralizes,
It disperses performed polymer in 263g deionized water under the high-speed stirred of 1000r/min, 3.8g (0.063 mole) ethylenediamine is added
The secondary rear chain extension of 12g (0.067 mole) 3,5- diethyl toluene diamine, high-speed stirred is added in chain extension afterwards, high-speed stirred 0.5h
Solvent is removed under reduced pressure in 1h, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension.
Experimental result test and analysis:
Experimental test procedures
1. emulsion film ATR infrared test: using Fourier infrared spectrograph.
2. emulsion film membrance casting condition: lotion is formed a film naturally after drying, and 60 DEG C of drying 2h, the glue film after drying does following survey
It takes temperature sign；
3. water-fast solvent resistance test:
Glue film is cut into 30mm × 30mm size.Deionized water is immersed at 25 DEG C, weighs it afterwards for 24 hours before immersion in ethyl alcohol
Mass change afterwards.
The calculation method of rate of body weight gain is as follows:
Rate of body weight gain=(m2-m1)/m1 × 100%
Wherein, m1 and m2 is respectively the quality for immersing front and back sample.
Analysis of experimental results:
By taking embodiment 1 as an example, Tables 1 and 2 is listed respectively on the basis of 45% water-soluble amine chain extension ratio, uses oil
Dissolubility diamines carry out secondary chain extension different proportion parameter and corresponding film forming matter it is water-fast/solvent resistance.
1 oil-soluble diamines of table carries out the different proportion design of secondary chain extension
2 oil-soluble diamines difference chain extension ratio of table is water-fast to film forming matter/influence of solvent resistance
| Sample number into spectrum | Water/% | Ethyl alcohol/% | 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 object
Water-fast/solvent resistance is crossed to optimum value, and obviously more more excellent than the film forming physical performance merely with water-soluble diamines chain extension, this
Illustrate the apparent effect that the secondary chain extension of oil-soluble diamines plays 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 lotion infrared spectroscopy carries out peak-fit processing, then calculates separately and obtains carbamic acid ester carbonyl group and urea groups carbonyl
The relative absorbance peak area accounting data of base, the results are shown in Table 3.
The infrared absorption peak area of table 3 different oil-soluble diamines chain extension ratio lotion carbamic acid ester carbonyl groups 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, illustrate the effectiveness of amine chain extension on the basis of water-soluble amine chain extension,
It further increases.This obvious verifying oil-soluble diamines effectively diffuses into inside polyurethane latex grain oleophylic really and occurs two
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 (13)
1. a kind of preparation method of the aqueous polyurethane dispersing liquid of secondary rear chain extension, it includes following steps:
Step 1), by one of relative molecular mass 500-4000 polymer diatomic alcohol or polymer polyatomic alcohol or a variety of heatings
To 100-130 DEG C, vacuum dehydration 1-2 hours；
Step 2) is cooled to 60-80 DEG C of addition diisocyanate, reacts 0.5-1 hours under nitrogen protection；
Suitable catalyst is added in step 3), reacts 1-3 hours at 60-90 DEG C, obtains the reactant of clear；
Hydrophilic chain extender, small molecule chain extender are added in the reactant of step 3) by step 4), use the reactant of step 3)
The solvent adjustment reaction system viscosity of 0.1-30wt% reacts 1-3 hours at 60-90 DEG C, obtains clarifying sticky performed polymer；
Step 5) is cooled to the 40-70 DEG C of neutralizer neutralization being added selected from C2-C4 tertiary amine or three-level hydramine, adjusts performed polymer
PH value in 6-8；
Step 6) disperses performed polymer in deionized water under 800-2000 revs/min of high-speed stirred, is added and is selected from level-one
Or the water-soluble rear chain extender of the C2-C4 diamines of second level, under high-speed stirred after chain extending reaction 0.5-2 hour, wherein after water solubility
NCO molar ratio is 0.01-0.8:1 in chain extender active function groups and performed polymer；
Step 7), it is that 0.02-1:1 is selected from C1-C3 alkyl toluene base diamines that NCO molar ratio in active function groups and performed polymer, which is added,
Or the oil-soluble rear chain extender of C1-C3 hetero atom alkyl toluene base diamines, it is secondary under high-speed stirred after chain extending reaction 0.5-2 it is small
When；40-70 DEG C is removed under reduced pressure solvent, obtains the aqueous polyurethane dispersing liquid of secondary rear chain extension；
Wherein, polymer diatomic alcohol or polymer polyatomic alcohol: hydrophilic chain extender: the molar ratio of small molecule chain extender is 1:0.1-1:
0.1-1, and polymer diatomic alcohol, polymer polyatomic alcohol, hydrophilic chain extender and small molecule chain extender total mole number and two isocyanides
The mole ratio of acid esters is 1:2-1.
2. preparation method according to claim 1, which is characterized in that the diisocyanate is toluene diisocynate
Ester, isophorone diisocyanate, hexamethylene diisocyanate, methyl diphenylene diisocyanate, dicyclohexyl methyl hydride two
One of isocyanates, naphthalene diisocyanate, paraphenylene diisocyanate, benzene dimethylene diisocyanate or a variety of mixing.
3. preparation method according to claim 1, which is characterized in that the catalyst be dibutyl tin dilaurate,
One of stannous octoate or a variety of mixing.
4. preparation method according to claim 1, which is characterized in that the hydrophilic chain extender is 2,2- dihydroxymethyl third
One of acid, 2,2- dimethylolpropionic acid, ethylenediamine base ethanesulfonic acid sodium, second dihydroxy ethanesulfonic acid sodium or a variety of mixing.
5. preparation method according to claim 1, which is characterized in that the small molecule chain extender is ethylene glycol, Isosorbide-5-Nitrae-
Butanediol, 3- methyl pentanediol, diglycol, 2- methyl propanediol, neopentyl glycol, 1,6-HD, trihydroxy methyl third
One of alkane, propylene glycol or a variety of mixing.
6. preparation method according to claim 1, which is characterized in that the solvent is acetone, butanone, N, N- dimethyl
One of formamide, N-Methyl pyrrolidone or a variety of mixing.
7. preparation method according to claim 1, which is characterized in that the neutralizer is triethylamine, triethanolamine, three
One of n-butylamine or a variety of mixing.
8. preparation method according to claim 7, which is characterized in that the neutralizer uses diethanol amine or/and hydrogen
Sodium oxide molybdena replaces.
9. preparation method according to claim 1, which is characterized in that the water-soluble rear chain extender is ethylenediamine, fourth
Diamines, N, one of N- dimethyl-ethylenediamine or a variety of mixing.
10. preparation method according to claim 9, which is characterized in that the water-soluble rear chain extender using pentanediamine,
One of hexamethylene diamine, cyclohexanediamine, isophorone diamine, piperazine or a variety of mixing replace.
11. preparation method according to claim 1, which is characterized in that the oil-soluble rear chain extender is 3,5- diethyl
One of base toluenediamine, 3,5- dimethythiotoluene diamine or a variety of mixing.
12. preparation method according to claim 11, which is characterized in that the oil-soluble rear chain extender uses 2- first
Base-pentanediamine, the chloro- 4,4'- diphenylmethanediamiand of 3,3'- bis-, the bis- Zhong Ding aminobenzenes of 1,4-, the bis- Zhong Ding amino two of 4,4'-
Phenylmethane, N, one of bis- sec-amyl cyclohexane diamines of N'- or a variety of mixing replace.
13. a kind of aqueous polyurethane dispersing liquid of any one of -12 preparation method preparations according to claim 1.
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| CN114574990B (en) * | 2022-03-16 | 2023-11-17 | 长乐恒申合纤科技有限公司 | Preparation method of easy-to-dye and easy-to-shape spandex fiber |
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