CN109608605A - A kind of ion-non-ion aqueous polyurethane dispersion preparation - Google Patents
A kind of ion-non-ion aqueous polyurethane dispersion preparation Download PDFInfo
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- CN109608605A CN109608605A CN201711377755.3A CN201711377755A CN109608605A CN 109608605 A CN109608605 A CN 109608605A CN 201711377755 A CN201711377755 A CN 201711377755A CN 109608605 A CN109608605 A CN 109608605A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- 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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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
The invention discloses a kind of ion-non-ion aqueous polyurethanes to disperse preparation.Existing aqueous polyurethane dispersion has the shortcomings that compatibility is poor, chemical resistance is insufficient.The present invention first prepares pure ionic aqueous polyurethane dispersion, recycle polyether diamine that non-ionic hydrophilic group is introduced into polyurethane molecular chain by rear chain extension mode, the most chain extension after water-soluble polyamine afterwards, is prepared for ion-non-ion aqueous polyurethane dispersion；The non-ionic hydrophilic group of aqueous polyurethane dispersion is led to by rear chain extension mode and is introduced into polyurethane molecular chain.Stability, compatibility and the chemical resistance that ion prepared by the present invention-non-ion aqueous polyurethane dispersion has had, while there is high mechanical property, it is suitable for a variety of substrates such as fabric, leather and paper.
Description
Technical field
The present invention relates to aqueous polyurethane technical field, specifically a kind of ion-non-ion aqueous polyurethane point
Granular media preparation method.
Background technique
Polyurethane material is because containing a large amount of polar group and active reactive group on its macromolecular chain, such as to a variety of substrates
Fabric, timber, rubber, metal, paper, plastics etc. all have good active force, therefore polyurethane material has been widely used for
The every field such as coating, finishing agent, adhesive.But it is influenced in recent years by various countries' environmental regulation and consumer demand, people
Increasingly pay close attention to green, the environmentally friendly feature of various chemicals material.Compared with solvent borne polyurethane material, aqueous polyurethane tool
There is nontoxic, free from environmental pollution, production and uses the features such as safe.Aqueous polyurethane product and solvent borne polyurethane product phase at present
Than the disadvantages of there are mechanical property deficiencies, poor solvent resistance, water resistance.
In order to improve the various performances of aqueous polyurethane product, in hard segment structure, the soft segment knot to aqueous polyurethane molecule
Structure, cross-linked structure carry out except various design studies, are more focused on to hydrophilic radical type in polyurethane molecular chain and content
Design studies this is because hydrophilic radical is the key factor of aqueous polyurethane Water-borne modification, while being also the main of influence performance
One of factor.
Patent CN102325816A discloses a kind of functionalized polyurethane polyurea dispersions, utilizes isocyanate-reactive
Ionic, non-ionic hydrophilic group are introduced on base polyurethane prepolymer for use as molecular backbone by group, then are dispersed emulsification and are obtained
Aqueous polyurethane polyurea dispersions containing epoxy-functional.Patent CN102046682A discloses a kind of Hdyrophilic polyurethane painting
Layer, wherein the polyurethane-urea as the end of the chain and contains ionic parent using the copolymer unit by polyethylene oxide and polypropylene oxide
Water base group, polyoxyethylene ether non-ionic hydrophilic compound used are introduced into polyurethane molecular chain in precondensation stage, Zhi Houzai
It emulsifies to obtain hydrophilic polyurethane coatings through chain, water dispersion.Patent CN103703041A describes a kind of based on polyester polyol
Aqueous polyurethane polyurea dispersions, ionic and non-ionic hydrophilic group are first also introduced into base polyurethane prepolymer for use as molecule
On main chain, then emulsify to obtain aqueous polyurethane polyurea dispersions by water dispersion.Patent CN107207693A discloses a kind of water
Property dispersions of polyurethanes, in the presence of being at least one pyrrolidones, and first passing through isocyanate-reactive group will be from
Subtype, non-ionic hydrophilic group are introduced on base polyurethane prepolymer for use as molecular backbone, then postmenstruation dispersion and emulsion, water-soluble di
Chain extension obtains aqueous polyurethane dispersion after amine.
The ionic and non-ionic hydrophilic group of above-mentioned existing aqueous polyurethane dispersion are all to first pass through isocyanates
Reactive group is introduced on base polyurethane prepolymer for use as molecular backbone, then finally obtains the aqueous poly- of various performances through water dispersion emulsification
Urethane dispersion.The aqueous polyurethane dispersion prepared using such method, although introducing one on polyurethane molecular main chain
Fixed non-ionic hydrophilic group, but that still there is compatibilities is poor, solvent resistant is poor, performance is insufficient for obtained dispersions of polyurethanes
The disadvantages of, especially pure its compatibility of ionic aqueous polyurethane dispersion, chemical resistance is obviously insufficient.
Summary of the invention
The technical problem to be solved by the present invention is to overcome existing aqueous polyurethane dispersion compatibility is poor, chemical resistance not
The disadvantages of sufficient, provides a kind of ion-non-ion aqueous polyurethane dispersion preparation, first prepares the aqueous poly- ammonia of ionic
Non-ionic hydrophilic group is introduced into polyurethane molecular chain by ester dispersion using rear chain extension mode, most afterwards through water solubility two
Chain extension after first amine prepares high molecular weight, ion-nonionic phenotype aqueous polyurethane dispersion；Drawn by rear chain extension mode
The aqueous polyurethane dispersion for entering non-ionic hydrophilic group has higher compatibility, stability, and point of aqueous polyurethane
Son amount is opposite to be further increased, and dispersions obtained mechanical property also further improves.
For this purpose, the technical solution adopted by the present invention are as follows: a kind of ion-non-ion aqueous polyurethane dispersion preparation side
Method, the ion-non-ion aqueous polyurethane dispersion non-ionic hydrophilic group are introduced into aqueous poly- by rear chain extension mode
On urethane strand, step includes:
1) ionic aqueous polyurethane dispersion is prepared
A) polyisocyanate compound is added in polymer polyatomic alcohol and catalyst carries out polymerization reaction, reaction temperature is extremely
50-90 DEG C, insulation reaction 0.5-3h, catalyst amount are the 0.05-0.5% of current reactant quality, catalysis at such a temperature
Agent is selected from: tertiary amine catalyst or organo-metallic compound；
B) small molecule chain extender, ionic hydrophilic chain extender and solvent is added, obtains the base polyurethane prepolymer for use as of hydrophilic modifying,
Solvent usage is the 5-30% of current reactant quality, adjusts reaction system viscosity using solvent, guarantees that reaction is gone on smoothly；
C) on demand, electrical neutralizer is added, ionic hydrophilic chain extender is neutralized；
D) it under the high-speed stirred of 500-3000rpm, disperses the base polyurethane prepolymer for use as of hydrophilic modifying in deionized water
Form ionic aqueous polyurethane dispersion；
2) non-ionic hydrophilic group introducing prepares ion-non-ion aqueous polyurethane dispersion
E) chain extension after polyether diamine chain extender carries out is added in the resulting ionic aqueous polyurethane dispersion of step d), instead
15-60min is answered, chain extending reaction after water-soluble polyamine chain extender carries out is subsequently added into, reacts 15-60min；
F) solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion；
Wherein, ion-non-ion aqueous polyurethane is made of following components according to mass ratio:
15-40% polyisocyanate compound, is selected from: aliphatic, alicyclic, aromatic series or araliphatic degree of functionality >=2
Polyisocyanates；
45-75% polymer polyatomic alcohol, is selected from: molal weight is the polyester polyols of 500 to 4000g/mol, degree of functionality >=2
Alcohol, polyether polyol, polycarbonate polyol, polyurethane polyol, polyacrylate polyol, polyester polyacrylate are polynary
Alcohol, polyurethane polyacrylate polyalcohol, polyurethane polyureas ester polyol or polyurethane polyureas ethoxylated polyhydric alcohol；
0.5-8% small molecule chain extender, is selected from polyol small molecule chain extender, and molal weight is less than 400g/
Mol, degree of functionality are 2 to 4；
0.5-4% ionic hydrophilic chain extender, ionic or the hydrophilic chain extension of potential ionic selected from tool hydroxyl or amido
Agent, degree of functionality are 2 to 4；
0-6% electrical property neutralizer；
0.5-6% polyether diamine chain extender, degree of functionality >=2 of polyether diamine chain extender, molal weight be 200 to
3000g/mol；
0.5-3% water solubility polyamine chain extender, degree of functionality >=2 of water-soluble polyamine chain extender, molal weight are small
In 400g/mol.
As the preferred of above-mentioned preparation method, in step b), it is hydrophilic that small molecule chain extender, the ionic with hydroxyl is added
After chain extender and solvent, 1-3h is reacted at 50-90 DEG C, obtains the base polyurethane prepolymer for use as of hydrophilic modifying.
As the another preferred of above-mentioned preparation method, in step b), small molecule chain extender and solvent is first added, in 50-90
1-3h is reacted at DEG C, cools to 35-60 DEG C, is added and is reacted 20-60min with amido ionic hydrophilic chain extender, obtains parent
The modified base polyurethane prepolymer for use as of water.
As the preferred of above-mentioned preparation method, polyisocyanate compound is selected from: degree of functionality be 2 aliphatic, it is alicyclic,
One or more of aromatic series, araliphatic polyisocyanate.
As the preferred of above-mentioned preparation method, polyisocyanate compound is selected from: hexamethylene diisocyanate (HDI),
Isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), two hexamethylenes
Dicyclohexylmethane diisocyanate, detergent alkylate -2,4- diisocyanate, cyclohexyl diisocyanate, tri-methyl hexamethylene two
Isocyanates, paraphenylene diisocyanate, benzene dimethylene diisocyanate, tetramethylene diisocyanate or durol diformazan
The one or more of group diisocyanate.
As the preferred of above-mentioned preparation method, the polymer polyatomic alcohol is selected from: molal weight is 500 to 4000g/
The one or more for the polymer polyatomic alcohol that mol and its degree of functionality are 2.
As the preferred of above-mentioned preparation method, the polymer polyatomic alcohol is selected from: molal weight is 600 to 3000g/
The one or more for the polymer polyatomic alcohol that mol and its degree of functionality are 2.
As the preferred of above-mentioned preparation method, the molal weight of the polymer polyatomic alcohol is 600 to 3000g/mol, choosing
From: polyhexamethylene adipate glycol, polybutylene glyool adipate, polyethylene glycol adipate glycol, polyadipate are new
Pentadiol ester glycol, polyadipate diglycol esterdiol, polycaprolactone glycol, poly- carbonic acid hexylene glycol esterdiol, poly- second
One or more of glycol, polypropylene glycol or polytetrahydrofuran ether glycol.
As the preferred of above-mentioned preparation method, small molecule chain extender is selected from: 60 to 400g/mol, degree of functionality be 2 to 3 it is more
The one or more of hydroxy compounds.
As the preferred of above-mentioned preparation method, small molecule chain extender is selected from: ethylene glycol, 1,4-butanediol, neopentyl glycol, one
One of diglycol ethylene, 3- methyl pentanediol, propylene glycol, 2- methyl propanediol, 1,6- hexylene glycol, trimethylolpropane or
It is several.
As the preferred of above-mentioned preparation method, ionic hydrophilic chain extender is selected from: degree of functionality be 2 ionic or it is potential from
Subtype hydrophilic chain extender, ionic group can be cation or anionic nature, with isocyanate-reactive group degree of functionality
It is hydroxyl or amido for suitable isocyanate-reactive group.
As the preferred of above-mentioned preparation method, ionic hydrophilic chain extender is selected from: N methyldiethanol amine, dihydroxymethyl third
Acid, dimethylolpropionic acid, ethylenediamine base ethylsulfonic acid sodium, Isosorbide-5-Nitrae-dihydroxy butane -2- sodium sulfonate, α, ω-polypropylene glycol-two
One or more of amine-sulfopropyl sodium salt.
As the preferred of above-mentioned preparation method, ionic hydrophilic chain extender is selected from N methyldiethanol amine, by being selected from sulphur
The electrical neutralizer reaction of one or more of sour dimethyl ether or glacial acetic acid, is converted to potential ionic group.
As the preferred of above-mentioned preparation method, ionic hydrophilic chain extender is selected from: dihydromethyl propionic acid, dihydroxymethyl fourth
One or more of acid, ethylenediamine base ethylsulfonic acid sodium, Isosorbide-5-Nitrae-dihydroxy butane -2- sodium sulfonate, by being selected from triethylamine, three
The electrical neutralizer of one or more of ethanol amine, dimethylethanolamine, diisopropyl ethyl amine, sodium hydroxide reacts, and turns
It is melted into potential ionic group.
As the preferred of above-mentioned preparation method, the polyether diamine molal weight is 200 to 3000g/mol, amido
Degree of functionality is 2.
As the preferred of above-mentioned preparation method, the polyether diamine molal weight is 200 to 2000g/mol, amido
Degree of functionality is 2.
As the preferred of above-mentioned preparation method, polyether diamine chain extender is selected from: by the polyethylene oxide of primary amine groups sealing end, being gathered
The one or more of propylene oxide or polyoxyethylene oxypropylene mixed type compound, it is total that ethyoxyl sum is greater than propoxyl group
Number.
As the preferred of above-mentioned preparation method, the molal weight of the water-soluble polyamine chain extender is less than 400g/
Mol, and degree of functionality is 2.
As the preferred of above-mentioned preparation method, the molal weight of the water-soluble polyamine chain extender is 60 to 400g/
Mol, and degree of functionality is 2.
Water-soluble polyamine chain extender is selected from: molal weight be 60 arrive 400g/mol, ethylenediamine, butanediamine, pentanediamine, oneself
Diamines, cyclohexanediamine, N, one or more of N- dimethyl-ethylenediamine, isophorone diamine, piperazine.
As the preferred of above-mentioned preparation method, catalyst is selected from: triethylenediamine, bis- (dimethylamino ethyl) ethers, it is double-
(3- dimethyl propylene amino) amine, three (dimethylaminopropyl) amine, N, N- dimethyl benzylamine, N, N- dimethyl cyclohexyl amine, bis- (2- diformazans
Amino-ethyl) ether, N, N, N', N'- tetramethyl Alkylenediamine, triethylamine, N, N- dimethyl benzylamine, solid amine, N-ethylmorpholine,
N-methylmorpholine, N, N '-diethyl piperazine, triethanolamine, pyridine, N are N '-dimethyl pyridine, dibutyl tin dilaurate, pungent
One or more of sour stannous.
As the preferred of above-mentioned preparation method, solvent, which is selected from, is not involved in the Conventional solvents of reaction, with adjusting reaction system
Viscosity guarantees that reaction is gone on smoothly.
Preferred as above-mentioned preparation method, the catalyst is dibutyl tin dilaurate or stannous octoate；Described
Solvent is one of acetone or butanone.
Ion-non-ion aqueous polyurethane dispersion that preparation method of the present invention provides, the dispersions of polyurethanes point
Shown in subformula such as formula (I):
Wherein,The aqueous polyurethane molecule knot of ionic aqueous polyurethane dispersion is formed for dispersion in water
Structure formula, R thereon1Represent ionic hydrophilic group group (or neutralization salt forming group of potential type ionic group)；X and z is epoxy third
Radix, y are epoxy ethyl number, and y > x+z.
The present invention first prepares pure ionic aqueous polyurethane dispersion, recycles polyether diamine will be non-by rear chain extension mode
Ionic hydrophilic group is introduced into polyurethane molecular chain, and finally to prepare ion-non-ionic for chain extension after water-soluble polyamine
Aqueous polyurethane dispersion.Secondary parent has been carried out to polyurethane latex grain by the non-ionic hydrophilic group that rear chain extension mode introduces
Water is modified, and introduced polyethylene oxide and polypropylene oxide segments is substantially distributed in emulsion particle surface, to further be promoted
The stability of aqueous polyurethane dispersion, and significantly improve the compatibility of aqueous polyurethane dispersion, chemical resistance.
With the addition of polyether diamine, polyurethane molecular has carried out first time chain, and polyurethane molecular amount increases；It adds
Chain extension after water-soluble polyamine rear chain extender carries out then has carried out second of polyurethane molecular chain chain effect, polyurethane molecular
Amount further increases.After twice after chain extension effect, the mechanical property of aqueous polyurethane is significantly promoted, therefore it is specific
Using when show excellent comprehensive performance.
Ion prepared in accordance with the present invention-non-ion aqueous polyurethane dispersion is suitable for fabric, leather, paper, wood
The a variety of substrates of material, metal, can be used as coating, finishing agent, adhesive, coating etc., be preferably suitable to fabric, leather and paper substrate.
Specific embodiment
Technical solution of the present invention is described further below with reference to embodiment.
The present invention is that a kind of ion-non-ion aqueous polyurethane disperses preparation, and the ion-is non-ion aqueous
The non-ionic hydrophilic group of dispersions of polyurethanes is introduced on aqueous polyurethane strand by rear chain extension mode, and step includes:
1) ionic aqueous polyurethane dispersion is prepared
A) polymer polyatomic alcohol is added in dry reactor, vacuum dehydration 1-2h, then passes to nitrogen at 100-120 DEG C
Gas cools to 50-70 DEG C；Polyisocyanate compound is added at 50-70 DEG C, adjusts reaction temperature to 50-90 DEG C, in the temperature
Lower insulation reaction 0.5-1h is spent, catalyst (0.05-0.5% that catalyst amount is current reactant quality) is added, continues
1-2h is reacted at 50-90 DEG C, catalyst is selected from: tertiary amine catalyst or organo-metallic compound；
B) small molecule chain extender, ionic hydrophilic chain extender and solvent is added, obtains the base polyurethane prepolymer for use as of hydrophilic modifying,
Solvent usage is the 5-30% of current reactant quality, guarantees that reaction is gone on smoothly using solvent adjustment reaction system viscosity；
Ionic hydrophilic chain extender is selected from: the ionic hydrophilic chain extender with hydroxyl or amido reactive group；
If the isocyanate-reactive group of ionic hydrophilic chain extender is hydroxyl, by this hydrophilic expansion of oh type ionic
Chain agent, small molecule chain extender are added in the reactant of step a), while guaranteeing reaction using solvent adjustment reaction system viscosity
It goes on smoothly, solvent usage is the 5-30% of current reactant quality, reacts 1-3h at 50-90 DEG C, obtains hydrophilic modifying
Base polyurethane prepolymer for use as；
If the isocyanate-reactive group of ionic hydrophilic chain extender is amido, small molecule chain extender is added to step
In rapid reactant a), while guaranteeing that reaction is gone on smoothly using solvent adjustment reaction system viscosity, solvent usage is current anti-
The 5-30% for answering amount of substance reacts 1-3h at 50-90 DEG C, system is then cooled to 35-60 DEG C, this amino-type ion is added
Type hydrophilic chain extender hydrophilic chain extender reacts 20-60min, obtains the base polyurethane prepolymer for use as of hydrophilic modifying；
C) to 35-60 DEG C, according to specific requirements, electrical neutralizer is added to the hydrophilic expansion of potential ionic in adjustment system temperature
Chain agent is neutralized, and the neutralization time is 5-15min；
D) it under the high-speed stirred of 1000-2000rpm, disperses the base polyurethane prepolymer for use as of hydrophilic modifying in deionized water
Form ionic aqueous polyurethane dispersion；
2) non-ionic hydrophilic group introducing prepares ion-non-ion aqueous polyurethane dispersion
E) chain extension after polyether diamine chain extender carries out is added in the resulting ionic aqueous polyurethane dispersion of step d), instead
15-40min is answered, chain extending reaction after water-soluble polyamine chain extender carries out is subsequently added into, reacts 15-30min；
F) solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion；
Wherein, ion-non-ion aqueous polyurethane is made of following components according to mass ratio:
15-40% polyisocyanate compound, is selected from: aliphatic, alicyclic, aromatic series or araliphatic degree of functionality >=2
Polyisocyanates；
45-75% polymer polyatomic alcohol, molal weight are 500 to 4000g/mol, and the polyester polyol of degree of functionality >=2 is gathered
Ethoxylated polyhydric alcohol, polyurethane polyol, polyacrylate polyol, polyester polyacrylate polyalcohol, gathers polycarbonate polyol
Urethane polyacrylate polyol, polyurethane polyureas ester polyol or polyurethane polyureas ethoxylated polyhydric alcohol；
0.5-8% small molecule chain extender, is selected from polyol small molecule chain extender, and molal weight is less than 400g/
Mol, degree of functionality are 2 to 4；
0.5-4% ionic hydrophilic chain extender, ionic or latent ionic hydrophilic chain extender selected from tool hydroxyl or amido,
Degree of functionality is 2 to 4；
0-6% electrical property neutralizer；
0.5-6% polyether diamine chain extender, degree of functionality >=2 of polyether diamine chain extender, molal weight be 200 to
3000g/mol；
0.5-3% water solubility polyamine chain extender, kind degree of functionality >=2 of water-soluble polyamine chain extender, molal weight
Less than 400g/mol.
Embodiment 1
By 70g polybutylene glyool adipate (molal weight 3000g/mol) at 120 DEG C vacuum dehydration 2h；So
After be passed through nitrogen, be cooled to 50 DEG C, 18g toluene di-isocyanate(TDI) be added, 0.5h is reacted at 70 DEG C, it is sub- that 0.05g octanoic acid is added
Tin, continuation react 2h at 70 DEG C；2.5g dihydromethyl propionic acid is added, 4.5g neopentyl glycol, 20g acetone react at 75 DEG C
1.5h obtains the base polyurethane prepolymer for use as of hydrophilic modifying；It is cooled to 60 DEG C, is added in 2g triethylamine and 5min, in the height of 1000rpm
It disperses performed polymer in 230g deionized water under speed stirring and forms dispersion liquid, 0.4g polyether diamine JEFFAMINE is then added
D230 (molal weight 230g/mol, 1.6g polyether diamine JEFFAMINE HK511 (molal weight 220g/mol, propoxyl group
Number is 1.2, and ethoxy radix is that 2), propoxyl group number is 2.5) to react 40min；Then 1g ethylenediamine, the reaction of 0.5g piperazine is added
15min；Solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion.
Embodiment 2
By 30g polyethylene glycol adipate glycol (molal weight 1500g/mol), 20g polyneopentyl glycol adipate
Glycol (molal weight 1500g/mol), 10g polypropylene glycol (molal weight 1500g/mol) vacuum dehydration at 115 DEG C
1.5h；Nitrogen is then passed to, is cooled to 70 DEG C, 28g isoflurane chalcone diisocyanate is added, 45min is reacted at 90 DEG C, is added
0.1g dibutyl tin dilaurate, continuation react 1.5h at 90 DEG C；2.7g 1,4-butanediol, 10g butanone, at 90 DEG C is added
Lower reaction 1h；35 DEG C are cooled to, is added 6g ethylenediamine base ethylsulfonic acid sodium solution (solid content 50%), 60min is reacted, obtains
The base polyurethane prepolymer for use as of hydrophilic modifying；It disperses performed polymer in 185g deionized water under the high-speed stirred of 1500rpm and is formed
Dispersion liquid, 4g polyether diamine JEFFAMINE HK511 is then added, and (molal weight 220g/mol, propoxyl group number are 1.2, second
Oxygroup number is 2) to react 35min；Then 1g butanediamine is added, 1.3g isophorone diamine reacts 20min；Solvent is sloughed in decompression,
Obtain ion-non-ion aqueous polyurethane dispersion.
Embodiment 3
By 15g polycaprolactone glycol (molal weight 1000g/mol), 35g polyethylene glycol adipate glycol (mole matter
Amount is 1000g/mol) the vacuum dehydration 2h at 105 DEG C；Nitrogen is then passed to, is cooled to 70 DEG C, it is different that 20g hexa-methylene two is added
Cyanate, 10g isophorone diisocyanate react 1h at 85 DEG C, and 0.08g dibutyl tin dilaurate is added, and continue
1h is reacted at 85 DEG C；2.8g N methyldiethanol amine, 5.7g diglycol is added, 5g butanone reacts 2h at 80 DEG C,
Obtain the base polyurethane prepolymer for use as of hydrophilic modifying；It is cooled to 55 DEG C, is added in 6g glacial acetic acid and 15min, in the high-speed stirring of 2000rpm
It mixes lower disperse performed polymer in 300g deionized water and forms dispersion liquid, 3g polyether diamine JEFFAMINE ED600 is then added
(molal weight 600g/mol, propoxyl group number are 3.6, and ethoxy radix is 9) to react 30min；Then 0.5g hexamethylene diamine, 2g is added
Cyclohexanediamine reacts 25min；Solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion.
Embodiment 4
By 40g polybutylene glyool adipate (molal weight 3000g/mol), 26g polyneopentyl glycol adipate
Glycol (molal weight 3000g/mol), 6g polyethylene glycol (molal weight 1500g/mol) vacuum dehydration at 120 DEG C
1.5h；Nitrogen is then passed to, is cooled to 65 DEG C, 5.2g hexamethylene diisocyanate, 10g diphenylmethane diisocyanate is added
Ester reacts 0.5h at 80 DEG C, and 0.2g stannous octoate is added, and continuation reacts 1.5h at 80 DEG C；2.5g 3- methylpent two is added
Alcohol, 0.5g trimethylolpropane, 15g acetone, react 2h at 70 DEG C；50 DEG C are cooled to, 4.5g α, ω-polypropylene glycol-is added
Diamines-sulfopropyl sodium salt (molal weight 550g/mol, solid content 90%) reacts 20min, obtains the poly- ammonia of hydrophilic modifying
Ester performed polymer；It disperses performed polymer in 150g deionized water under the high-speed stirred of 1000rpm and forms dispersion liquid, be then added
1g polyether diamine JEFFAMINE D400 (molal weight 430g/mol, propoxyl group number be 6.1), 4g polyether diamine
(molal weight 2000g/mol, propoxyl group number are 6 to JEFFAMINE ED2003, and ethoxy radix is 39) to react 15min；Then
0.8g isophorone diamine is added and reacts 30min；Solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion.
Embodiment 5
By 5g polyethylene glycol (molal weight 2000g/mol), 10g polypropylene glycol (molal weight 2000g/mol), 40g
Polytetrahydrofuran ether glycol (molal weight 2000g/mol) vacuum dehydration 1h at 115 DEG C；Nitrogen is then passed to, is cooled to
60 DEG C, 31g dicyclohexyl methyl hydride diisocyanate, 2g tetramethylene diisocyanate is added, reacts 45min at 55 DEG C, adds
Enter 0.4g stannous octoate, 0.1g dibutyl tin dilaurate, continuation reacts 2h at 55 DEG C；0.3g dihydromethyl propionic acid is added,
1.4g ethylene glycol, 0.3g trimethylolpropane, 25g acetone, react 2.5h at 60 DEG C；45 DEG C are cooled to, 1g ethylenediamine is added
Base ethylsulfonic acid sodium solution (solid content 50%) reacts 30min, obtains the base polyurethane prepolymer for use as of hydrophilic modifying；It is cooled to 35
DEG C, be added 0.5g triethanolamine in and 10min, disperse 125g deionized water for performed polymer under the high-speed stirred of 1500rpm
Middle formation dispersion liquid, 4g polyether diamine JEFFAMINE HK511 is then added, and (molal weight 220g/mol, propoxyl group number are
1.2, ethoxy radix be 2.0), (molal weight 900g/mol, propoxyl group number are 2g polyether diamine JEFFAMINE ED900
6.0, ethoxy radix is 12.5) to react 20min；Then 3g piperazine is added and reacts 15min；Solvent is sloughed in decompression, and it is non-to obtain ion-
Ionic aqueous polyurethane dispersion.
Embodiment 6
By 15g polycaprolactone glycol (molal weight 600g/mol), the poly- carbonic acid hexylene glycol esterdiol (molal weight of 20g
600g/mol), 10g polytetrahydrofuran ether glycol (molal weight 600g/mol) vacuum dehydration 1.5h at 105 DEG C；Then lead to
Enter nitrogen, be cooled to 55 DEG C, 30g toluene di-isocyanate(TDI), 10g tetramethyl benzhydryl vulcabond is added, at 60 DEG C
1h is reacted, 0.1g stannous octoate, 0.2g dibutyl tin dilaurate is added, continuation reacts 1h at 60 DEG C；1g dihydroxy first is added
Base butyric acid, 8g neopentyl glycol, 30g acetone, reacts 3h at 65 DEG C；40 DEG C are cooled to, 4g ethylenediamine base ethylsulfonic acid sodium is added
Solution (solid content 50%) reacts 45min, obtains the base polyurethane prepolymer for use as of hydrophilic modifying；45 DEG C are cooled to, it is different that 1g bis- is added
In ethylamine and 5min, performed polymer is scattered in be formed in 230g deionized water under the high-speed stirred of 2000rpm and is dispersed
Liquid, then be added 1.5g polyether diamine JEFFAMINE D400 (molal weight 430, propoxyl group number be 6.1), 3.5g polyethers two
(molal weight 900, propoxyl group number are 6.0 to amine JEFFAMINE ED900, and ethoxy radix is 12.5) to react 25min；Then plus
Enter 0.6g butanediamine, 1.4g isophorone diamine, reacts 20min；Solvent is sloughed in decompression, and it is non-ion aqueous poly- to obtain ion-
Urethane dispersion.
For comparative example 1-6 other than not adding polyether diamine chain extender, other implementation conditions are that corresponding embodiment 1-6 is identical
Implementation condition, be specifically shown in Table 1.
Chain extension designs after 1 comparative example of table polyether diamine chain extender different from embodiment
Experimental result test and analysis:
Experimental test procedures:
1. molecular weight test: being measured using gel permeation chromatograph.
2. compatibility stability: in 10ml in graduated test tube, 5ml lotion is added with dropper, is then slowly added into 1ml
0.5% CaCl2Solution sufficiently shakes up on rear holding test tubes frame, observes afterwards in for 24 hours, if is divided into, precipitates, flocculates
Phenomenon.
3. 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 solvent resistant
Property test and Mechanics Performance Testing.
4. solvent resistance is tested: glue film is cut into 30mm × 30mm；It is immersed in ethyl alcohol at 25 DEG C, weighs it afterwards for 24 hours and soaking
Enter the mass change of front and back.Rate of body weight gain calculation method 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.
5. mechanical property: being measured using electronic universal material testing machine.
Analysis of experimental results: comparative analysis has been carried out to each embodiment, table 2 lists each embodiment respectively and do not use, adopts
With the performance comparison of each aqueous polyurethane dispersion obtained under chain extension after polyether diamine chain extender.
Table 2: the performance comparison for each aqueous polyurethane dispersion that embodiment and comparative example are made
From table 2 it can be seen that the aqueous polyurethane dispersion that each embodiment after polyether diamine chain extender after chain extension, obtains
Molecular weight, calcium salt compatibility stability, solvent resistant alcohol performance and mechanical property etc. be all improved.Illustrate through rear chain extension
Non-ionic hydrophilic group is introduced into polyurethane molecular chain by mode, and the non-ionic hydrophilic of introducing is rolled into a ball to polyurethane latex grain
Secondary hydrophilic modifying is carried out, the polyethylene oxide and polypropylene oxide segments of introduced polyether diamine chain extender are substantially distributed in
Emulsion particle surface, obtained aqueous polyurethane dispersion have higher molecular weight, stability, chemical resistance, mechanical property etc.
Performance.
Protection scope of the present invention is not limited to above-described embodiment, and any other forms under present invention enlightenment are all
It is that there is same or similar technical solution with the present invention, it is within the scope of the present invention.
Claims (10)
1. a kind of ion-non-ion aqueous polyurethane disperses preparation, which is characterized in that the non-ionic water of the ion-
Property dispersions of polyurethanes non-ionic hydrophilic group be introduced on aqueous polyurethane strand by rear chain extension mode, step packet
It includes:
1) ionic aqueous polyurethane dispersion is prepared
A) polyisocyanate compound is added in polymer polyatomic alcohol and catalyst carries out polymerization reaction, reaction temperature to 50-90
DEG C, insulation reaction 0.5-3h, catalyst amount are the 0.05-0.5% of current reactant quality, catalyst choosing at such a temperature
From: tertiary amine catalyst or organo-metallic compound；
B) small molecule chain extender, ionic hydrophilic chain extender and solvent is added, obtains the base polyurethane prepolymer for use as of hydrophilic modifying, solvent
Dosage is the 5-30% of current reactant quality；
C) on demand, electrical neutralizer is added, ionic hydrophilic chain extender is neutralized；
D) it under the high-speed stirred of 500-3000rpm, disperses the base polyurethane prepolymer for use as of hydrophilic modifying in deionized water and is formed
Ionic aqueous polyurethane dispersion；
2) non-ionic hydrophilic group introducing prepares ion-non-ion aqueous polyurethane dispersion
E) chain extension after polyether diamine chain extender carries out, reaction is added in the resulting ionic aqueous polyurethane dispersion of step d)
15-60min is subsequently added into chain extending reaction after water-soluble polyamine chain extender carries out, reacts 15-60min；
F) solvent is sloughed in decompression, obtains ion-non-ion aqueous polyurethane dispersion；
Wherein, ion-non-ion aqueous polyurethane dispersion is made of following components according to mass ratio:
15-40% polyisocyanate compound, is selected from: aliphatic, alicyclic, aromatic series or araliphatic degree of functionality >=2 it is more
Isocyanates；
45-75% polymer polyatomic alcohol, is selected from: molal weight be 500 to the 4000g/mol, polyester polyol of degree of functionality >=2,
Polyether polyol, polycarbonate polyol, polyurethane polyol, polyacrylate polyol, polyester polyacrylate polyalcohol,
Polyurethane polyacrylate polyalcohol, polyurethane polyureas ester polyol or polyurethane polyureas ethoxylated polyhydric alcohol；
0.5-8% small molecule chain extender is selected from polyol small molecule chain extender, and molal weight is less than 400g/mol,
Degree of functionality is 2 to 4；
0.5-4% ionic hydrophilic chain extender, ionic or potential ionic hydrophilic chain extender selected from tool hydroxyl or amido, official
Energy degree is 2 to 4；
0-6% electrical property neutralizer；
0.5-6% polyether diamine chain extender, degree of functionality >=2 of polyether diamine chain extender, molal weight are 200 to 3000g/
mol；
0.5-3% water solubility polyamine chain extender, degree of functionality >=2 of water-soluble polyamine chain extender, molal weight are less than
400g/mol。
2. the method according to claim 1, wherein small molecule chain extender is added, with hydroxyl in step b)
After ionic hydrophilic chain extender and solvent, 1-3h is reacted at 50-90 DEG C, obtains the base polyurethane prepolymer for use as of hydrophilic modifying.
3. small molecule chain extender and solvent is first added the method according to claim 1, wherein in step b),
1-3h is reacted at 50-90 DEG C, cools to 35-60 DEG C, adds the ionic hydrophilic chain extender reaction 20-60min with amido,
Obtain the base polyurethane prepolymer for use as of hydrophilic modifying.
4. according to the method in any one of claims 1 to 3, which is characterized in that the polyisocyanate compound choosing
From: hexamethylene diisocyanate, isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
Dicyclohexyl methyl hydride diisocyanate, detergent alkylate -2,4- diisocyanate, cyclohexyl diisocyanate, trimethyl six are sub-
Methyl diisocyanate, paraphenylene diisocyanate, benzene dimethylene diisocyanate, tetramethylene diisocyanate, tetramethyl
One or more of xylylene diisocyanate；
The molal weight of the polymer polyatomic alcohol is 600 to 3000g/mol, and be selected from: polyhexamethylene adipate glycol gathers oneself
Succinate adipate glycol, polyethylene glycol adipate glycol, polyneopentyl glycol adipate glycol, one contracting diethyl of polyadipate
Glycol esterdiol, polycaprolactone glycol, poly- carbonic acid hexylene glycol esterdiol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol
One or more of.
5. according to the method in any one of claims 1 to 3, which is characterized in that small molecule chain extender is selected from: ethylene glycol,
1,4-butanediol, neopentyl glycol, diglycol, 3- methyl pentanediol, propylene glycol, 2- methyl propanediol, 1,6- hexylene glycol,
One or more of trimethylolpropane.
6. according to the method in any one of claims 1 to 3, which is characterized in that ionic hydrophilic chain extender is selected from: N- first
Base diethanol amine, dihydromethyl propionic acid, dimethylolpropionic acid, ethylenediamine base ethylsulfonic acid sodium, Isosorbide-5-Nitrae-dihydroxy butane -2- sulfonic acid
Sodium, α, one or more of ω-polypropylene glycol-diamines-sulfopropyl sodium salt.
7. according to the method described in claim 6, it is characterized in that, ionic hydrophilic chain extender be selected from N methyldiethanol amine,
By the electrical neutralizer reaction selected from one or more of dimethyl sulfate ether or glacial acetic acid, it is converted to potential ionic group.
8. according to the method described in claim 6, it is characterized in that, ionic hydrophilic chain extender is selected from: dihydromethyl propionic acid, two
One or more of hydroxymethylbutyrate, ethylenediamine base ethylsulfonic acid sodium, Isosorbide-5-Nitrae-dihydroxy butane -2- sodium sulfonate, by being selected from
The electrical of one or more of triethylamine, triethanolamine, dimethylethanolamine, diisopropyl ethyl amine or sodium hydroxide neutralizes
Agent reaction, is converted to potential ionic group.
9. according to the method in any one of claims 1 to 3, which is characterized in that
Polyether diamine chain extender is selected from: polyethylene oxide, polypropylene oxide or the polyethylene oxide epoxy third blocked by primary amine groups
The one or more of alkane mixed type compound, ethyoxyl sum are greater than propoxyl group sum；
Water-soluble polyamine chain extender is selected from: molal weight be 60 arrive 400g/mol, ethylenediamine, butanediamine, pentanediamine, oneself two
Amine, cyclohexanediamine, N, one or more of N- dimethyl-ethylenediamine, isophorone diamine, piperazine.
10. according to the method in any one of claims 1 to 3, which is characterized in that the catalyst is selected from: three ethylenes
Diamines, bis- (dimethylamino ethyl) ethers, double-(3- dimethyl propylene amino) amine, three (dimethylaminopropyl) amine, N, N- dimethylbenzyl
Amine, N, N- dimethyl cyclohexyl amine, bis- (2- dimethylaminoethyl) ethers, N, N, N', N'- tetramethyl Alkylenediamine, triethylamine, N,
N- dimethyl benzylamine, solid amine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine, triethanolamine, pyridine, N, N '-two
One or more of picoline, dibutyl tin dilaurate, stannous octoate；The solvent is acetone or butanone.
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