CN108676144A - A kind of Waterproof Breathable aqueous polyurethane dispersion and its preparation method and application - Google Patents
A kind of Waterproof Breathable aqueous polyurethane dispersion and its preparation method and application Download PDFInfo
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- CN108676144A CN108676144A CN201810569770.6A CN201810569770A CN108676144A CN 108676144 A CN108676144 A CN 108676144A CN 201810569770 A CN201810569770 A CN 201810569770A CN 108676144 A CN108676144 A CN 108676144A
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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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides one kind for waterproof moisture permeating fabric coating aqueous polyurethane dispersion and its preparation method and application.The aqueous polyurethane dispersion introduces the strongly hydrophilic pendant hydroxyl groups of clustering by special small molecule chain extender on main chain, and it is formed and is acted synergistically by slightly water-wet ehter bond on it and branch, to be conducive to the one-way movement of moisture from inside to outside in fabric, it balances hydraulic pressure and the problem of moisture-inhibiting mutually restricts, while obtaining good waterproof and water vapour permeability.
Description
Technical field
The invention belongs to water-base polyurethane material fields, and in particular to a kind of Waterproof Breathable aqueous polyurethane dispersion and
Preparation method and use.
Background technology
As the improvement of people's living standards, outdoor sports increase, the requirement to outdoor sports apparel is higher and higher, waterproof
Moisture-inhibiting is a main trend.Polyurethane resin is currently used waterproof and moisture permeability resin, but waterproof and moisture permeability polyurethane tree at present
There is also the poor problems of penetrability for fat.
It is 11500g/24h to study amount of sweat of the finder in activity, and fabric takes around 4000g/m2/ correspondence for 24 hours
Vapor transfer rate；Meanwhile in order to reach ideal waterproof effect, also requiring the hydrostatic pressing of fabric that must not be less than 5.58KPa.Fabric is resistance to quiet
The raising of hydraulic pressure value often causes the decline of vapor transfer rate.Therefore, there is certain resistance to hydrostatic pressure performance in guarantee coated fabric
Under the premise of, how to improve vapor transfer rate just becomes correlative study person's focus of attention.Domestic and international researcher passes through on strand
The technologies such as hydrophilic segment or group of introducing, are prepared for Waterproof Breathable type Aqueous Polyurethane Coating Agent, and especially low VOC's is aqueous poly-
Urethane coating agent, but the introducing of hydrophilic segment or group also brings along the decline of water resistance.
US6613867 discloses a kind of preparation method of penetrability aqueous polyurethane, and component A is isocyanic acid bifunctional
Ester, B component are ethylene glycol, diethylene glycol, 1,3-PD, and component C is glycol of the molecular weight less than 400, diamines, amino alcohol, D
Group is divided into ethoxy alcohol or ethyoxyl/propoxyl group copolyol.US2011312237A1 discloses a kind of with water vapour permeability heat
The preparation method of plasticity waterborne polyurethane resin (is wherein copolymerized more using polyol and polyethoxy glycol as soft segment
First alcohol is the copolymer of ethyoxyl and C3-C6 alkoxies), polyethoxy glycol 70-97%, polyol 3- in two kinds of soft segments
30%.The shortcomings that above-mentioned aqueous polyurethane using polyethylene glycol as air-permeable layer is that the emulsion viscosity for preparing is bigger, construction
Technique is poor, and resin keeps washing fastness also poor due to not hydrolysis.
CN10883803 disclose it is a kind of use the polyalcohol containing polyethylene oxide side chains as hydrophilic monomer, made with PEG1000
For soft segment, come the aqueous polyurethane dispersion prepared, the water vapour permeability and mechanical strength of the dispersion are preferable, but do not improve
Water pressure resistance performance and resin viscosity is larger.
Above-mentioned publication shows that Waterproof Breathable waterborne polyurethane resin uses poly- ethoxy on main chain mostly at present
Base dihydric alcohol, or hydrophilic group is introduced on side chain.But experiment is, it was also found that when ethyoxyl (- EO-) hydrophilic radical exists
When on main chain, although-EO- segments can play the role of transmitting the moisture-inhibiting of hydrone well, due to the hydrophily of its own, with
The increase of-EO- segments on main chain, the water pressure resistance performance of resin declines obviously.When hydrophilic-EO- groups are on side chain, though
Right water pressure resistance and penetrability can obtain certain balance, but when improving water vapour permeability, water pressure resistance performance is often by shadow
It rings.Therefore, in the case where ensureing certain water pressure resistance performance, penetrability how is improved, and performance after keeping fabric repeatedly to wash
It is not remarkably decreased, these demands all propose correlative study person new challenge.
Invention content
The primary purpose of the present invention is that providing a kind of novel Waterproof Breathable aqueous polyurethane dispersion.The dispersion
Introduce the strongly hydrophilic pendant hydroxyl groups of clustering on main chain by special small molecule chain extender, and by it with it is weak on branch
Hydrophily ehter bond forms synergistic effect, is conducive to the one-way movement of moisture from inside to outside in fabric, balances hydraulic pressure and moisture-inhibiting phase
The problem of mutually restricting, so as to obtain good waterproof and water vapour permeability simultaneously.
Another object of the present invention is to provide the preparation methods of the aqueous polyurethane waterproof and moisture permeability dispersion.
It is still another object of the present invention to provide the applications of the Waterproof Breathable aqueous polyurethane dispersion.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of Waterproof Breathable coating aqueous polyurethane dispersion, including prepared by following raw material：
A, at least two diisocyanate, addition 19-29wt%, preferably 22-25wt%；
B, at least two polyether Glycols and/or polyester diol, addition 28-41wt%, preferably 32-38wt%；
C, the polyethers or polyester polyol of at least one degree of functionality >=3, addition 10-20wt%, preferably 10.5-
15wt%；
D, at least one small molecule polyol chain extender containing active hydrogen, addition 0.5-4wt%, preferably 1.5-
3wt%；
E, at least one nonionic hydrophilic chain extender containing active hydrogen, addition 14-30wt%, preferably 20-25wt%；
F, at least two small molecule polyamine chain extender containing active hydrogen, addition 3.8-5.3wt%, preferably 4-
5wt%；
G, at least two auxiliary agent, including two or more in antioxidant, light stabilizer and ultraviolet absorber, addition
0.2-2.0wt%, preferably 0.4-1.0wt%；
Above-mentioned raw materials weight by waterborne polyurethane resin admittedly containing weight in terms of.
In the present invention, component a be selected from aliphatic and/or alicyclic isocyanate, preferably isophorone diisocyanate,
Two kinds in 1,6- hexyl diisocyanates, dicyclohexyl methyl hydride diisocyanate and tetramethyl xylylene diisocyanate or
It is a variety of, more preferable dicyclohexyl methyl hydride diisocyanate and 1,6- hexyl diisocyanates.Two kinds of isocyanates can cooperate with instead
It answers, is controlled convenient for dispersant molecule structure design and molecular weight, to make the comprehensive performance of dispersion more preferably.
In the present invention, component b is selected from PolyTHF dihydric alcohol, polyethylene glycol dihydric alcohol, polypropylene glycol diols and gathers
Two or more in ethylene glycol and 1,2-propylene glycol dihydric alcohol；Preferred number average molecular weight be 300~3000 poly- third dihydric alcohol and/or
Two or more in PolyTHF dihydric alcohol；A kind of poly- third dihydric alcohol that more preferably number-average molecular weight is 1500~2500 and
The mixture for the different molecular weight PolyTHF dihydric alcohol that two kinds of number-average molecular weights are 1000~2500, wherein poly- third dihydric alcohol
It is 0.2 with PolyTHF diol mixture mass ratio:1~0.7:1.Poly- third dihydric alcohol is at low cost, reaction is mild, poly- tetrahydrochysene
Furans dihydric alcohol is had excellent performance, and the two collocation uses the requirement that can meet mass production.
In the present invention, component c preferred, polyethers polyalcohols, the polyglycerol of more preferable molecular weight 2000 and 3000, most preferably
The polyglycerol of molecular weight 3000.The polyglycerol of three officials is introduced from molecular architecture and molecular weight control, it is good obtaining
While fabric feeling, textile hydrostatic pressure performance can also be obviously improved.
In the present invention, component d molecular weight is 30-200；Selected from 1,3- propylene glycol, 1,4- butanediols, diglycol,
It is one or more in neopentyl glycol, 1,6- hexylene glycols and 1,4-CHDM, preferred 1,4-butanediol and/or 1,6- oneself
Glycol.
In the present invention, component e molecular weight is 500-3000；Selected from TegoChemie companiesD-3403、
The Ymer of Perstrop companiesTMOne or more in N120 and the MPEG1200 of South Korea's Lotte Company, preferably Perstrop is public
The Ymer of departmentTMN120.Ehter bond is introduced in molecular side chain by N120 etc., weakly water-wet ehter bond can be with strong hydrophilicity in chain extender
Hydroxyl formed synergistic effect, to mutually restricted between active balance hydraulic pressure and penetrability the problem of.
In the present invention, component f molecular weight is 30-300；Selected from ethylenediamine, hexamethylene diamine, 4,4- diphenyl methanes two
Two kinds in amine, hydroxyethyl ethylenediamine, di-n-butylamine, isophorone diamine and bis- [(trihydroxy methyl) methylamino] propane of 1,3-
Or a variety of, the mixture or 1 of preferably 1,3- bis- [(trihydroxy methyl) methylamino] propane and ethylenediamine, 3- bis- [(trihydroxy methyls)
Methylamino] propane and isophorone diamine mixture；The structure of bis- [(trihydroxy methyl) methylamino] propane of wherein 1,3-
Formula is：
Pendant hydroxyl groups containing 6 strong hydrophilicities in bis- [(trihydroxy methyl) methylamino] the propane structures of 1,3- introduced, it is main
Position in chain where the chain extender just has accumulated the hydroxyl of cluster, can form stronger hydrogen bond action with water, adsorption moisture,
An effective channel is provided for the conduction of hydrone, is conducive to the one-way movement of moisture from inside to outside, hence it is evident that improve resin
Water vapour permeability, while different water vapour permeabilities can be obtained by adjusting chain extender addition.
In the present invention, two or more of component g in hindered amine, hindered phenol, preferably antioxidant 1010 and light are stablized
The combination of agent 292.
In the present invention, catalyst need to be added when preparing resin, catalyst includes but not limited to that organo-bismuth or organic zinc are urged
The leading organic bismuth catalyst 8108 of agent, the preferably U.S., additive amount are well known catalytic amount.
In the present invention, containing admittedly for the dispersion is 30~45wt%, and the grain size of preferably 35-40wt%, dispersion are 30
~100nm, preferably 40~80nm.
Preparation method in the present invention includes following preparation process：
(1) component a, b, c, e hybrid reactions generate isocyanate-terminated prepolymer, 75-85 DEG C of reaction temperature；
(2) component d, acetone, catalyst are added in prepolymer to be reacted, further increase the molecular weight of prepolymer, instead
75-85 DEG C of temperature is answered, is cooled down after reaching theoretical NCO%, acetone dilution is added；
(3) the acetone dilute solution of addition component g, wherein acetone addition are 5-8 times of g, are added and go under high speed shear
Ionized water is disperseed；
(4) the water dilute solution progress chain extension of addition component f, wherein water addition are 3-5 times of f, are taken off after chain extension
Acetone obtains aqueous polyurethane dispersion product.
In the present invention, the dispersion prepared as stated above can be used for waterproof moisture permeating fabric coating, which can answer
It is used for sweat shirt, outdoor clothes, fire-entry suit, military uniform, leisure wind coat, Breathable rain cape, base camp tent, sleeping bag, postal packet, protection
Product, medical insurance articles for use field.
The positive effect of the present invention is mainly reflected in the following aspects：
(1) Waterproof Breathable effect of the invention is realized by a kind of novel aqueous polyurethane hydrophilic-structure：It is poly- to mix
Ethoxylated polyhydric alcohol is main chain, and the portion on main chain introduces the strongly hydrophilic pendant hydroxyl groups of clustering, while in the side chain
Slightly water-wet ehter bond is introduced, the two can form synergistic effect, balance the problem of mutually being restricted between hydraulic pressure and penetrability, have
Conducive to the one-way movement of moisture from inside to outside, to realize waterproof and the function of moisture-inhibiting simultaneously；
(2) the fabric resistance to hydrostatic pressure ＞ 5100mmH of the resin have been brushed2O, rate of perviousness ＞ 6000g/m2/ for 24 hours, it washes five times
Later, water pressure resistance and water vapour permeability, which decline, is no more than 18% and 4%；
(3) simple production process of the present invention, easy to operation, safe and non-toxic.
Specific implementation mode
Test method in the present invention is as follows：
Admittedly containing test method：It takes in appropriate lotion container made of masking foil, weighs at 150 DEG C before and after 20min
Weight change calculates its solid content.
Grain size test method：Using Malvern particle instrument.
PH test methods：Using pH meter.
Viscosity determining procedure：Using BROOKFIELD viscosity apparatus, No. 3 rotors, rotating speed 30rpm.
Appearance test method：Eye, which is seen, to be judged.
Rate of perviousness：By ASTM-E96-05, test condition is 50 DEG C, 23%RH, 5-10h, 2.5m/s wind speed, unit g/
m2/24h。
Hydrostatic pressing：By GB/T4744-1997, unit mmH2O。
Washing 5 times：By GB/T8629-2001, washing machine is machine-washed five times, and 40 DEG C of water temperature, time 45min is repeated 5 times, water
Pressure and water vapour permeability are dropped by less than 80% as qualification.
Pliability：It is classified by 1-5,5 indicate optimal, and 1 indicates worst, and judgement is touched by hand.
Surface dry degree：It is classified by 1-5,5 indicate optimal, and 1 indicates worst, and judgement is touched by hand.
Resilience：It is classified by 1-5,5 indicate optimal, and 1 indicates worst, and judgement is touched by hand.
The construction technology that fabric coating is prepared with dispersion is as follows：
Slurry is scratched on the nylon cloth of demifacet dumb light with dise knife, 150 DEG C of drying 1min, upper two knife, ensures two knives altogether
Total starching amount is in 20~30g/m2.Sample conserves in 50 DEG C of baking ovens to be tested afterwards for 24 hours.
Fabric coating construction formula is as follows：
The raw material used in embodiment is as follows：
(dicyclohexyl methyl hydride diisocyanate, NCO% contents are about 32.0% to HMDI, ten thousand China's chemistry
Group Plc)；
(1, hexamethylene-diisocyanate, NCO% contents are about 50% to HDI, ten thousand magnificent chemical groups shares
Co., Ltd)；
PPG2000 (polypropylene glycol, hydroxyl value 56mgKOH/g, number-average molecular weight ≈ 2000, degree of functionality 2, the big chemistry in east)；
PTMG2000 (polytetrahydrofuran ether glycol, hydroxyl value 56mgKOH/g, number-average molecular weight 2000, degree of functionality 2, Yantai
Hua Da chemistry)；
PTMG1000 (polytetrahydrofuran ether glycol, hydroxyl value 112mgKOH/g, number-average molecular weight 1000, degree of functionality 2, cigarette
Platform Hua Da chemistry)；
YmerTMN120 (polyethylene oxide ether glycol, hydroxyl value 110mgKOH/g, number-average molecular weight ≈ 1000, Sweden
Perstorp companies)；
MN3050 (polyglycerol, hydroxyl 56mgKOH/g, number-average molecular weight=3000, degree of functionality 3, the big chemistry in east)；
HDO (1,6- hexylene glycol, BASF Corp. of Germany)；
BDO (1,4-butanediol, BASF Corp. of Germany)；
IPDA (isophorone diamine, BASF Corp. of Germany)；
EDA (ethylenediamine, BASF Corp. of Germany)；
1,3- bis- [(trihydroxy methyl) methylamino] propane (chain extender, Dalian U.S. logical sequence Technology Co., Ltd.)；
292 (light stabilizer, Cibas of the U.S.)；
1010 (antioxidant, Cibas of the U.S.)；
U300 (polyurethanes association thickener, Wanhua Chemical Group Co., Ltd.)；
U605 (polyurethanes association thickener, Wanhua Chemical Group Co., Ltd.)；
268 (isocyanate curing agent, Wanhua Chemical Group Co., Ltd.)；
Silok43 (hand feeling agent, Guangzhou Si Luoke chemical companies)；
Stock white (color stuffing, Jiangsu richness are resistant to Pi Hua companies).
Embodiment 1
40g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flask
HMDI、25.2gHDI、70g N120、35g PPG2000、50gPTMEG2000、15gPTMEG1000、30g
MN3050 reaches 6.13% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 6g BDO, 0.08136g catalyst 8108 and the dilution of 40g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.51% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 54g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
656g deionized waters are added.
By 2g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 48g deionized waters, slowly
In addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 35wt%, grain size by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of 40nm.
Embodiment 2
41g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
25gHDI、60g N120、36g PPG2000、47gPTMEG2000、17gPTMEG1000、30g
MN3050 reaches 6.53% theoretical NCO% after reacting 1h at 85 DEG C.
60 DEG C are cooled to, 7g BDO, 0.0789g catalyst 8108 and the dilution of 39.6g acetone is added, stirs evenly, rises
For temperature to 85 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.61% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 52.6g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35
℃。
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
637g deionized waters are added, obtain aqueous polyurethane dispersion.
By 2g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 48g deionized waters, slowly
In addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 35wt%, grain size by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of 60nm.
Embodiment 3
38g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
24gHDI、80g N120、50g PPG2000、60gPTMEG2000、15gPTMEG1000、38g
MN3050 reaches 4.41% theoretical NCO% after reacting 1h at 75 DEG C.
60 DEG C are cooled to, 3.5g BDO, 0.09255g catalyst 8108 and the dilution of 46g acetone is added, stirs evenly, rises
For temperature to 75 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 1.89% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 61g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
730g deionized waters are added, obtain aqueous polyurethane dispersion.
Bis- [(trihydroxy methyl) methylamino] propane of 4g isophorone diamine and 10g 1,3- are dilute with 56g deionized waters
It releases, is slowly added in system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of 30wt%, grain size 40nm.
Embodiment 4
50g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
26gHDI、50g N120、20g PPG2000、40gPTMEG2000、25gPTMEG1000、30g
MN3050 reaches 8.52% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 10g BDO, 0.0753g catalyst 8108 and the dilution of 37g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 3.33% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 50g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
609g deionized waters are added, obtain aqueous polyurethane dispersion.
By 3.5g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 54g deionized waters, are delayed
In slow addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 40wt%, grain by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of diameter 80nm.
Embodiment 5
30g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
20gHDI、35g N120、45g PPG2000、40gPTMEG2000、15gPTMEG1000、45g
MN3050 reaches 4.86% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 3.5g BDO, 0.07005g catalyst 8108 and the dilution of 35g acetone is added, stirs evenly, rises
For temperature to 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.49% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 46g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
568g deionized waters are added, obtain aqueous polyurethane dispersion.
By 1.5g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 46g deionized waters, are delayed
In slow addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 45wt%, grain by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of diameter 92nm.
Embodiment 6
40g is added in equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flaskHMDI、
25gHDI、80g N120、35g PPG2000、35gPTMEG2000、10gPTMEG1000、45g
MN3050 reaches 6.20% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 6g HDO, 0.0813g catalyst 8108 and the dilution of 40g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.84% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 54g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
640g deionized waters are added, obtain aqueous polyurethane dispersion.
By 3g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 52g deionized waters, slowly
In addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 30wt%, grain size by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of 42nm.
Comparative example 1
This comparative example is added without bis- [(trihydroxy methyl) methylamino] propane of 1,3-.To equipped with reflux condensing tube, thermometer
40g is added in churned mechanically four-hole boiling flaskHMDI、25.2gHDI、70g
N120,35g PPG2000,50g PTMEG2000,15gPTMEG1000,30g MN3050 reach after reacting 1h at 80 DEG C
6.13% theoretical NCO%.
60 DEG C are cooled to, 6g BDO, 0.0813g catalyst 8108 and the dilution of 40g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.51% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 54g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
642g deionized waters are added, obtain aqueous polyurethane dispersion.
4g ethylenediamines 16g deionized waters are diluted, are slowly added in system, 35 DEG C of isothermal reaction 5min, it will be obtained
Lotion vacuum distillation removes acetone, obtains solid content 30wt%, the apparent aqueous polyurethane emulsion of blue light of grain size 50nm.
Comparative example 2
PEG1000 is added in this comparative example, is added without N120.To equipped with reflux condensing tube, thermometer and churned mechanically four
40g is added in mouth flaskHMDI、25.2gHDI、70gPEG1000、35g PPG2000、
50g PTMEG2000,15gPTMEG1000,30g MN3050 reach 6.13% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 6g BDO, 0.08136g catalyst 8108 and the dilution of 40g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.51% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 54g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
656g deionized waters are added, obtain aqueous polyurethane dispersion.
By 2g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 48g deionized waters, slowly
In addition system, lotion obtained is evaporated under reduced pressure and removes acetone, obtains solid content 30wt%, grain size by 35 DEG C of isothermal reaction 5min
The apparent aqueous polyurethane emulsion of blue light of 45nm.
Comparative example 3
This comparative example uses single isocyanates.To equipped with reflux condensing tube, thermometer and churned mechanically four-hole boiling flask
Middle addition 50gHDI、70g PEG1000、35g PPG2000、50gPTMEG2000、15gPTMEG1000、
30g MN3050 reach 6.32% theoretical NCO% after reacting 1h at 80 DEG C.
60 DEG C are cooled to, 6g BDO, 0.0768g catalyst 8108 and the dilution of 38g acetone is added, stirs evenly, heats up
To 80 DEG C, 4.5~6.5h of reaction (75 DEG C of beginning timing) stops reaction when reaching 2.52% theoretical NCO%.It is cooled to 60
DEG C, the dilution of 51g acetone is added, is stirred 5min, performed polymer and acetone is made to be sufficiently mixed, and continue to be cooled to 30~35 DEG C.
1010/292 acetone soln is added, stirs 5min, makes to be uniformly mixed, 1200~1500rpm stirrings, in 6min
606g deionized waters are added, obtain aqueous polyurethane dispersion.
By 2g ethylenediamines and 10g 1, bis- [(trihydroxy methyl) methylamino] propane of 3- are diluted with 48g deionized waters, slowly
In addition system, obtained lotion is unstable, occurs solidification phenomenon after 12h.
Fabric coating is prepared with the dispersion in each embodiment and comparative example, the performance of sample is shown in Table 1 after construction：
Dispersion prepares fabric coating properties of sample in 1 embodiment and comparative example of table
By the performance data of comparative example 1 and embodiment 1 compares：It is compared with embodiment 1, the hydrostatic pressing of comparative example 1
Quite, rate of perviousness is poor, and performance declines notable after washing 5 times.That bis- [(the three hydroxyl first of 1,3- are not added mainly in comparative example 1
Base) methylamino] propane, which there is preferable hydrophilic water vapour permeability can effectively transmit hydrone.
By the performance data of comparative example 2 and embodiment 1 compares：It is compared with embodiment 1, the penetrability of comparative example 2
Preferably, water pressure resistance performance is excessively poor, and the dry and comfortable degree of coating surface and resilience are obviously poor.It is primarily due to poly- ammonia in comparative example 2
Ester resin backbone introduces N120s of the PEG1000 instead of nonionic hydrophile moiety, weak because N120 introduces ehter bond in molecular side chain
Hydrophilic ehter bond can be formed with the hydroxyl of strong hydrophilicity in above-mentioned special chain extender and be acted synergistically, and be conducive to moisture from inside to outside
One-way movement, so resin penetrability and water pressure resistance are all poorer than embodiment 1 in comparative example 2, and 2 emulsion viscosity of comparative example compared with
Greatly, it is not easy to implement work.
The foregoing is merely the section Example of the present invention, practical ranges not for the purpose of limiting the invention；If do not taken off
It from the spirit and scope of the present invention, modifies or equivalently replaces the present invention, should all cover in the claims in the present invention
In protection domain.
Claims (10)
1. a kind of Waterproof Breathable coating aqueous polyurethane dispersion, including prepared by the reaction of following raw material：
A, at least two diisocyanate, addition 19-29wt%, preferably 22-25wt%；
B, at least two polyether Glycols and/or polyester diol, addition 28-41wt%, preferably 32-38wt%；
C, the polyethers or polyester polyol of at least one degree of functionality >=3, addition 10-20wt%, preferably 10.5-15wt%；
D, at least one small molecule polyol chain extender containing active hydrogen, addition 0.5-4wt%, preferably 1.5-3wt%；
E, at least one nonionic hydrophilic chain extender containing active hydrogen, addition 14-30wt%, preferably 20-25wt%；
F, at least two small molecule polyamine chain extender containing active hydrogen, addition 3.8-5.3wt%, preferably 4-5wt%；
G, at least two auxiliary agent, including two or more in antioxidant, light stabilizer and ultraviolet absorber, addition 0.2-
2.0wt%, preferably 0.4-1.0wt%；
Above-mentioned raw materials weight by waterborne polyurethane resin admittedly containing weight in terms of.
2. dispersion according to claim 1, which is characterized in that component a is selected from aliphatic and/or alicyclic isocyanic acid
Ester, preferably isophorone diisocyanate, 1,6- hexyl diisocyanates, dicyclohexyl methyl hydride diisocyanate and tetramethyl
Two or more in xylylene diisocyanate, more preferable dicyclohexyl methyl hydride diisocyanate and 1, two isocyanide of 6- hexyls
Acid esters.
3. dispersion according to claim 1, which is characterized in that component b is selected from PolyTHF dihydric alcohol, polyethylene glycol
Two or more in dihydric alcohol, polypropylene glycol diols and polyethylene glycol-propylene glycol dihydric alcohol；Preferred number average molecular weight is
Two or more in 300~3000 poly- third dihydric alcohol and/or PolyTHF dihydric alcohol；A kind of more preferable number-average molecular weight
The different molecular weight PolyTHF two for being 1000~2500 for 1500~2500 poly- third dihydric alcohol and two kinds of number-average molecular weights
The mixture of first alcohol, wherein poly- third dihydric alcohol and PolyTHF diol mixture mass ratio are 0.2:1~0.7:1.
4. dispersion according to claim 1, which is characterized in that component c preferred, polyethers polyalcohols more preferably count equal molecule
The polyglycerol of amount 2000 and 3000, the most preferably polyglycerol of number-average molecular weight 3000.
5. dispersion according to claim 1, which is characterized in that component d number-average molecular weights are 30-200；Selected from 1,3- third
Glycol, 1,4- butanediols, diglycol, neopentyl glycol, 1,6-HD and one kind in 1,4 cyclohexane dimethanol or
It is a variety of, preferred 1,4-butanediol and/or 1,6- hexylene glycols.
6. dispersion according to claim 1, which is characterized in that component e number-average molecular weights are 500-3000；It is selected from
TegoChemie companiesThe Ymer of D-3403, Perstrop companyTMN120 and South Korea's Lotte Company
It is one or more in MPEG1200, the preferably Ymer of Perstrop companiesTM N120。
7. dispersion according to claim 1, which is characterized in that component f number-average molecular weights are 30-300；Selected from second two
Amine, hexamethylene diamine, 4,4- diphenylmethanediamiands, hydroxyethyl ethylenediamine, di-n-butylamine, isophorone diamine and 1,3- are bis-
Two or more in [(trihydroxy methyl) methylamino] propane, bis- [(trihydroxy methyl) methylamino] propane of preferably 1,3- and second
The mixture of diamines or 1, the mixture of 3- bis- [(trihydroxy methyl) methylamino] propane and isophorone diamine；Wherein 1,3-
The structural formula of bis- [(trihydroxy methyl) methylamino] propane is：
8. according to claim 1-7 any one of them dispersions, which is characterized in that the dispersion it is solid containing for 30~
The grain size of 45wt%, preferably 35-40wt%, dispersion are 30~100nm, preferably 40~80nm.
9. according to the preparation method of claim 1-8 any one of them dispersions, which is characterized in that walked comprising following preparation
Suddenly：
(1) component a, b, c, e hybrid reactions generate isocyanate-terminated prepolymer, 75-85 DEG C of reaction temperature；
(2) component d, acetone, catalyst are added in prepolymer to be reacted, further increase the molecular weight of prepolymer, reaction temperature
75-85 DEG C of degree, cools down after reaching theoretical NCO%, and acetone dilution is added；
(3) the acetone dilute solution of addition component g, wherein acetone addition are 5-8 times of g, and deionization is added under high speed shear
Water is disperseed；
(4) the water dilute solution progress chain extension of addition component f, wherein water addition are 3-5 times of f, take off acetone after chain extension,
Obtain aqueous polyurethane dispersion product.
10. dispersion prepared by the dispersion or claim 9 the method according to any one of claim 1-8 is answered
With the dispersion can be used for waterproof moisture permeating fabric coating, which can be applied to sweat shirt, outdoor clothes, fire-entry suit, army
Clothes, leisure wind coat, Breathable rain cape, base camp tent, sleeping bag, postal packet, protective articles, medical insurance articles for use field.
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