CN109970948A - A kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof - Google Patents
A kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof Download PDFInfo
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- CN109970948A CN109970948A CN201910283627.5A CN201910283627A CN109970948A CN 109970948 A CN109970948 A CN 109970948A CN 201910283627 A CN201910283627 A CN 201910283627A CN 109970948 A CN109970948 A CN 109970948A
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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
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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Abstract
The present invention relates to field of textiles, a kind of Gao Hangu anion aqueous polyurethane lotion and preparation method thereof is disclosed.The preparation method is the following steps are included: raw material preparation: polymerized monomer, viscosity modifier, adjuvant and water；Pre-polymerization；Chain extension；Sealing end；It emulsifies and Gao Hangu anion aqueous polyurethane product emulsion is made.The controllability of preparation method of the present invention is strong, and technique is smooth.It can be widely used for elastic bonding agent printing and the coating processing of all kinds of textile products using Gao Hangu anion aqueous polyurethane product emulsion prepared by this method.Suitable polyether lateral chain is introduced in the polyurethane high molecule, while significantly improving product emulsion solid content and stability, can also assign its lower viscosity and moderate film forming speed.Meanwhile suitable cross-linking type active termination, therefore its glue film elasticity foot, feel smooth, flexible are also introduced in the polyurethane high molecule tail base.
Description
Technical field
The present invention relates to the height of the elastic bonding agent printing and coating of all kinds of textile products processing to contain solid anion aqueous poly- ammonia
A kind of ester lotion, and in particular to Gao Hangu anion aqueous polyurethane lotion and preparation method thereof.
Background technique
In field of textiles, pigment printing and style coating technology are due to significant energy-saving feature and its rich and changeful
Product effect becomes one of textile printing and dyeing processing technology with fastest developing speed and most important developing direction.In recent years, disappear
It is extensive and in great demand for the approval for being knitted product to take market, however is suitable for the height of knitted fabric and textile pigment printing or covering with paint
Bullet, Gao Hangu aqueous high molecular are but still the bottleneck for limiting the development of this industrial field.Among these, with the height of excellent resilience
Technology of preparing and the good Related product of comprehensive performance containing solid anionic polyester type aqueous polyurethane macromolecule resin lotion are more
It is rare.Currently, the Related product based on the prior art mainly has aqueous (modification) polyacrylate, aqueous (modification) poly- ammonia
Ester, waterborne polyurethane modified polyacrylate etc., but these conventional products are generally existing is unsuitable for preparing because solid content is lower
The problems such as paint-printing colour size is with covering with paint, lacquer, colour wash, etc. processing, or not being suitable for knitted textile product because elastic poor.These aqueous high moleculars
Generally by by the copolymerization of various monomers, block or it be grafted, blocked, interpenetrating networks, the method for modifying such as blending come it is real
Existing.
Currently, the preparation method of polyurethane based water-based macromolecule and Gao Hangu aqueous polyurethane resin emulsion includes following several
Kind:
(1) preparation method of end hydroxy butadiene modified anion aqueous polyurethane, its raw material include polymerized monomer,
Modifying agent, adjuvant and water, in which: polymerized monomer includes polyether polyol, diisocyanate, anion chain extender, nonionic
Chain extender；Modifying agent is poly- along butadiene；Adjuvant includes polymerization catalyst, neutralizer and diluent.
" the synthesis and property of end hydroxy butadiene modified aqueous polyurethane as written by Yan little Mei, Shen Huifang, poplar mark et al.
Energy " (" coatings industry " the 4th phases of volume 42 in 2012) discloses the preparation method of end hydroxy butadiene modified aqueous polyurethane, it
Raw material in: polymerized monomer be polyether Glycols N220, isophorone diisocyanate and dihydromethyl propionic acid, ethylenediamine, 1,
4- butanediol；Modifying agent is that terminal hydroxy group is poly- along butadiene；Adjuvant includes the positive fourth tin of polymerization catalyst dilaurate two, neutralizer
Triethylamine, diluent acetone；Emulsification is deionized water.
The polybutadiene-modified anion aqueous polyurethane that this method is prepared has good dispersion stabilization, relative to
Unmodified anion aqueous polyurethane, glue film also have relatively good water resistance and low-temperature pliability.However, this method
The aqueous polyurethane of preparation is polyether-type structure, is not suitable for pigment printing processing；Its solid content is lower, is not also suitable for preparing
Elastic rubber cement.Further, since its content of polyether is higher, so that the water imbibition of material glue film is still up to 30% or so.
(2) preparation method of the high modified polyacrylate emulsion containing setting polyurethane, its raw material mainly include polyvalent alcohol,
Diisocyanate, alkyl acrylate, adjuvant and water.
As Qi Dongming, Chen Zhijie, Gao Yujie et al. disclose " micro suspension in patent application CN 201410211412.X
The method that polymerization prepares the polyurethane-modified polyacrylate emulsion copolymer of submicron order ", in its raw material: polyvalent alcohol is poly- four
Hydrogen furans glycol etc.；Diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenylmethane diisocyanates
Ester, hexamethylene diisocyanate, paraphenylene diisocyanate；Alkyl acrylate be butyl acrylate, methyl methacrylate,
Methacrylic acid, hydroxyethyl methacrylate, hydroxy-ethyl acrylate etc.；Adjuvant is catalyst dibutyltin cinnamic acid dibutyl lithium, draws
Send out agent azodiisobutyronitrile, polyethylene of dispersing agent alcohol, assistant for emulsifying agent hexadecane.
Isocyanates, polyalcohol are added in the acrylate monomer containing assistant for emulsifying agent by this method, and catalyst is added,
It heats up after pre-polymerization, chain extension, end-capping reagent is added, obtains oiliness monomer mixed solution；Initiator is added into oiliness monomer mixed solution, then
It goes in the aqueous solution of dispersing agent, carries out ultrasonic micro suspension；Fine suspension, which is heated up, and is reacted terminates, after cooling down, obtains
To PUA lotion.The high emulsion particle of modified polyacrylate containing setting polyurethane prepared is derived directly from the sub-micro liquid that monomer is blended
Drop, there is no monomer migration and diffusion processes as emulsion system, thus two class monomers are limited always in the course of the polymerization process
In drop phase, it is ensured that the abundant copolymerization of the two；In addition, high solids content can be relatively easily prepared in microsuspension polymerization technology
Polyurethane-modified polyacrylate emulsion copolymer.However, lacking crosslinkable acrylic ester monomer and poly- ammonia in this method formula
Not only adjustability is poor for the elasticity of ester chain link, but also polyether structure therein can also bring what the water resistance of material glue film reduced to ask
Topic；In addition, the oiliness initiator in emulsion particle also will cause, polymerization rate initiation is too fast, and reaction controllability is bad；System
In polyethylene of dispersing agent alcohol the problem of there are also Form aldehyde releases.
(3) preparation method of Gao Hangu aqueous polyurethane emulsion, its raw material mainly include polyvalent alcohol, diisocyanate
Ester, hydrophilic chain extender, adjuvant and water.
" preparation of high solid content aqueous polyurethane emulsion and its performance are ground as written by Wen Yanjia, Chen Hongling, Zhang Yu et al.
Study carefully " (" printing and dyeing assistant " the 3rd phases of volume 32 in 2015) disclose the preparation method of high solid content aqueous polyurethane emulsion, its raw material
In: polyvalent alcohol is polytetrahydrofuran diol (PTMG), and diisocyanate is toluene di-isocyanate(TDI) (TDI), hydrophilic chain extender
For dihydromethyl propionic acid (DMPA), adjuvant includes solvent butanone, catalyst dibutyltindilaurylmercaptide cinnamic acid and neutralizer triethylamine
Deng.
The high solid content aqueous polyurethane emulsion that this method is prepared has obvious multimodel particle size distribution, and viscosity is smaller, contains
Gu amount is up to 48%, and its glue film has moderate water resistance, tensile strength and elongation at break.However, this method preparation
Aqueous polyurethane is polyether-type structure, is not suitable for pigment printing processing, is not also suitable for preparing coating elasticity rubber cement.In addition,
Since its content of polyether is higher, so that the water resistance of material glue film cannot still be met the requirements.
As written by Sun Dongcheng, Chen Qiao " synthesis and characterization containing sulfonic/carboxyl polyurethane dispersion having high solids content "
(" Journal of Chemical Industry and Engineering " the 3rd phases of volume 61 in 2010) disclose the preparation method of polyurethane dispersion having high solids content lotion, its raw material
In: polyvalent alcohol is polyadipate hexylene glycol neopentyl glycol ester (PHNA), and diisocyanate is isophorone diisocyanate
(IPDI), hexamethylene diisocyanate (HDI), hydrophilic chain extender are sulfonate polyether Glycols (SPPG) and dihydroxymethyl third
Sour (DMPA), adjuvant includes solvent acetone, catalyst and neutralizer triethylamine etc..
The high solid content aqueous polyurethane emulsion that this method is prepared has obvious multimodel particle size distribution, and viscosity is smaller, contains
Gu amount is up to 50%, and its glue film has good soft and hard segments compatibility, and it is preferable to show that it has for lower glass transition temperature
Cold resistance.However, the aqueous polyurethane of this method preparation is needed using expensive and rare SPPG and HDI；Further, since it is poly-
Ether content is higher, so that the water resistance of material glue film cannot still be met the requirements.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of Gao Hangu anion aqueous polyurethane lotion and its preparation
Method.The controllability of the preparation method is strong, and technique is smooth.The Gao Hangu anion aqueous polyurethane lotion prepared using this method
Product can be widely used for elastic bonding agent printing and the coating processing of all kinds of textile products.It is introduced in the polyurethane high molecule appropriate
Polyether lateral chain can also assign its lower viscosity and moderate film forming speed while significantly improving product emulsion solid content
Degree.Meanwhile the present invention also introduces suitable cross-linking type active termination, therefore its glue film elasticity in the polyurethane high molecule tail base
Foot, feel smooth, flexible.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
The present invention provides a kind of preparation method of Gao Hangu anion aqueous polyurethane lotion, this method includes following step
It is rapid:
(1) pre-polymerization: carrying out prepolymerization reaction for polyester-diol and diisocyanate, polymerization catalyst, be made it is high containing Gu Yin from
Sub- Waterborne Polyurethane Prepolymer；
(2) chain extension: the Gao Hangu anion aqueous polyurethane performed polymer and chain extender, viscosity modifier, part is dilute
Agent reaction is released, Gao Hangu anion aqueous polyurethane intermediate is made, wherein the chain extender includes nonionic chain extender and yin
Ion chain extender；
(3) block: by the Gao Hangu anion aqueous polyurethane intermediate and blocking agent reaction, be made it is high containing Gu Yin from
Sub- aqueous polyurethane macromolecule；
(4) it emulsifies: will be in the Gao Hangu anion aqueous polyurethane macromolecule, neutralizer, remainder diluent, bath
Chain extender, water are mixed and are emulsified, and Gao Hangu anion aqueous polyurethane lotion is made；
Wherein, the molfraction of dosage of each component are as follows: diisocyanate 25, polyester-diol 8~10, nonionic chain extender 6
~8, anion chain extender 2~5, end-capping reagent 2~5, viscosity modifier 0.5~0.9, wherein polyester-diol, nonionic chain extender,
The sum of molfraction of anion chain extender and viscosity modifier is 18~22, and the molfraction of chain extender is that (25- is poly- in bath
Esterdiol molfraction-nonionic chain extender molfraction-anion chain extender molfraction-viscosity modifier that part
Number-end-capping reagent molfraction × 0.5) × (0.3~1.2)；
With total dosage of diisocyanate, polyester-diol, nonionic chain extender, anion chain extender and end-capping reagent for 100
Parts by weight meter, the dosage of the polymerization catalyst are 0.04~0.06 parts by weight；
The dosage of the neutralizer is 0.9~1.2 times of the anion chain extender weight；
The viscosity modifier be polyethylene glycol and the molecular weight that molecular weight is 200~600 be 1000~1500 it is linear
The mixture of polyethylene glycol methyl ether, and the molecular weight be 200~600 polyethylene glycol and the molecular weight be 1000~
The ratio between mole of 1500 linear polyethylene ethylene glycol monomethyl ether is 0.3~1.5:1, preferably 0.5~1:1；
The end-capping reagent is gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane
At least one of with γ-aminopropyltriethoxy diethoxy silane；
Chain extender is ethylenediamine and/or making methylpentamethylenediamine diamine in the bath.
Preferably, the operating process of step (1) are as follows:
(1.1) polyester-diol is put into reactor, is warming up to 70~80 DEG C；
(1.2) it puts into diisocyanate and maintains to stir, control temperature of reaction system is 75~85 DEG C, maintains to be stirred to react
15~30min；
(1.3) maintaining temperature of reaction system is 75~85 DEG C, and polymerization catalyst is at the uniform velocity put into 15~20min；
(1.4) heating up and controlling temperature of reaction system is 80~90 DEG C, 80~100min of insulation reaction, is made high and contains Gu Yin
Ion Waterborne Polyurethane Prepolymer.
Preferably, the operating process of step (2) are as follows:
(2.1) system of the Gao Hangu anion aqueous polyurethane performed polymer of step (1) preparation is cooled to 75~
85℃；
(2.2) it is uniformly added into viscosity modifier, anion chain extender in 10~20min, maintaining reaction temperature is 75~
85℃；
(2.3) control reaction temperature is 80~90 DEG C and continues to be stirred to react 20~40min, is cooled to 75~85 DEG C later
And continue to be stirred to react 80~100min；
(2.4) cooling down and controlling reaction temperature is 65~75 DEG C, be added nonionic chain extender and continuing be stirred to react 80~
100min, during being stirred to react, addition is no more than the diluent of 80 weight % of total amount several times, to control reaction system
Viscosity, be made Gao Hangu anion aqueous polyurethane intermediate.
Preferably, the operating process of step (3) are as follows:
(3.1) system of the Gao Hangu anion aqueous polyurethane intermediate of step (2) preparation is cooled to 55~
65℃；
(3.2) end-capping reagent is uniformly added into 10~20min, maintaining temperature later is 55~65 DEG C, it is stirred to react 50~
Gao Hangu anion aqueous polyurethane macromolecule is made in 70min.
Preferably, the operating process of step (4) are as follows:
(4.1) it is added in the high molecular system of Gao Hangu anion aqueous polyurethane prepared to step (3) remaining
Portion of diluent stirs and is cooled to 50 DEG C or less；
(4.2) neutralizer is added, and maintenance system temperature is 40~50 DEG C, stirs 15~20min；
(4.3) into mulser be added 20~35 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in the reactor of process (4.2) is added to process (4.3)
Mulser in, later maintain stirring 40~60min；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion is made.
Preferably, adipic acid/Isosorbide-5-Nitrae-that the polyester-diol is moisture content not higher than 2 ‰ and molecular weight is 1000~2000
The adipic acid that butanediol copolymer glycols, molecular weight are 2000~3000/diglycol copolymer glycols and molecular weight are 1500
The mixture of one or both of~2500 adipic acid/1,4- butanediol/diglycol copolymer glycols.
Preferably, the diisocyanate is toluene di-isocyanate(TDI) and/or isophorone diisocyanate.
Preferably, the polymerization catalyst is stannous octoate and/or dibutyl tin dilaurate.
Preferably, the nonionic chain extender is 1,4-butanediol and/or neopentyl glycol.
Preferably, the anion chain extender is dihydromethyl propionic acid and/or dimethylolpropionic acid.
Preferably, the diluent is at least one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
Preferably, the neutralizer is triethylamine.
Preferably, water used in step (4) is the soft water that total hardness is less than or equal to 50ppmCaO.
Preferably, the dosage of water and the diluent makes the Gao Hangu anion aqueous polyurethane lotion of preparation
Solid content is 50~55%.
It is described high containing solid anion aqueous poly- ammonia the present invention also provides a kind of Gao Hangu anion aqueous polyurethane lotion
Ester lotion is made by the above method.
Preferably, the solid content of the Gao Hangu anion aqueous polyurethane lotion is 50~55%.
Preferably, the viscosity of the Gao Hangu anion aqueous polyurethane lotion is to exist according to AFAM2008/10503 method
The delivery time measured under conditions of 23 DEG C, 4mm glasss was less than 100 seconds.
Through the above technical solutions, method of the present invention has the following advantages that and feature:
(1) macromolecule product of the preparation method preparation of Gao Hangu anion aqueous polyurethane lotion of the present invention is
Weak anionic type has excellent compatibility with common TEXTILE CHEMICALS, also has preferable compatibility with cationic auxiliary, have
Conducive to simplified technique for applying, shorten processing flow.
(2) even using multifunctional silane in the preparation method of Gao Hangu anion aqueous polyurethane lotion of the present invention
Join agent and active termination is carried out to polyurethane, solves the problems, such as that weak anionic macromolecule filming is poor；Simultaneously as sealing end
The molecular weight of product is smaller, is also beneficial to obtain the lesser Gao Hangu lotion of viscosity.
(3) right in water using diamines in the preparation method of Gao Hangu anion aqueous polyurethane lotion of the present invention
On a small quantity reserved polyurethane terminal isocyanate groups bathed in chain extension, effectively prevent the high viscosity phenomenon of reaction process.
(4) in the preparation method of Gao Hangu anion aqueous polyurethane lotion of the present invention using molecular weight it is smaller and
Functional chain extender (i.e. viscosity modifier) containing polyether lateral chain or polyether backbone draws into polyurethane side chain and skeleton structure
Enter a small amount of polyethers short chain, be equipped with substep echelon chain extension, the high molecular hydrophilic-structure distribution of product can be effectively controlled, help to obtain
Obtain the lotion of low viscosity.
(5) anion chain extension is used in the preparation method of Gao Hangu anion aqueous polyurethane lotion of the present invention
Agent, nonionic chain extender, polyethers chain extender (i.e. viscosity modifier), bath in chain extender, in three times to polyurethane intermediate product into
Row chain extension, facilitates the lotion for obtaining multimodel particle size distribution, and product emulsion viscosity is smaller.
(6) the macromolecule product glue of the preparation method preparation of Gao Hangu anion aqueous polyurethane lotion of the present invention
Film extensibility and elasticity are excellent, solid content is high, viscosity is low, transparency is good, and tool has been widely used.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of Gao Hangu anion aqueous polyurethane lotion of the present invention the following steps are included:
(1) pre-polymerization: carrying out prepolymerization reaction for polyester-diol and diisocyanate, polymerization catalyst, be made it is high containing Gu Yin from
Sub- Waterborne Polyurethane Prepolymer；
(2) chain extension: the Gao Hangu anion aqueous polyurethane performed polymer and chain extender, viscosity modifier, part is dilute
Agent reaction is released, Gao Hangu anion aqueous polyurethane intermediate is made, wherein the chain extender includes nonionic chain extender and yin
Ion chain extender；
(3) block: by the Gao Hangu anion aqueous polyurethane intermediate and blocking agent reaction, be made it is high containing Gu Yin from
Sub- aqueous polyurethane macromolecule；
(4) it emulsifies: will be in the Gao Hangu anion aqueous polyurethane macromolecule, neutralizer, remainder diluent, bath
Chain extender, water are mixed and are emulsified, and Gao Hangu anion aqueous polyurethane lotion is made.
In more preferably embodiment, the operating process of step (1) are as follows:
(1.1) polyester-diol is put into reactor, is warming up to 70~80 DEG C；
(1.2) it puts into diisocyanate and maintains to stir, control temperature of reaction system is 75~85 DEG C, maintains to be stirred to react
15~30min；
(1.3) maintaining temperature of reaction system is 75~85 DEG C, and polymerization catalyst is at the uniform velocity put into 15~20min；
(1.4) heating up and controlling temperature of reaction system is 80~90 DEG C, 80~100min of insulation reaction, is made high and contains Gu Yin
Ion Waterborne Polyurethane Prepolymer.
In more preferably embodiment, the operating process of step (2) are as follows:
(2.1) system of the Gao Hangu anion aqueous polyurethane performed polymer of step (1) preparation is cooled to 75~
85℃；
(2.2) it is uniformly added into viscosity modifier, anion chain extender in 10~20min, maintaining reaction temperature is 75~
85℃；
(2.3) control reaction temperature is 80~90 DEG C and continues to be stirred to react 20~40min, is cooled to 75~85 DEG C later
And continue to be stirred to react 80~100min；
(2.4) cooling down and controlling reaction temperature is 65~75 DEG C, be added nonionic chain extender and continuing be stirred to react 80~
100min, during being stirred to react, addition is no more than the diluent of 80 weight % of total amount several times, to control reaction system
Viscosity, be made Gao Hangu anion aqueous polyurethane intermediate.
In more preferably embodiment, the operating process of step (3) are as follows:
(3.1) system of the Gao Hangu anion aqueous polyurethane intermediate of step (2) preparation is cooled to 55~
65℃；
(3.2) end-capping reagent is uniformly added into 10~20min, maintaining temperature later is 55~65 DEG C, it is stirred to react 50~
Gao Hangu anion aqueous polyurethane macromolecule is made in 70min.
In more preferably embodiment, the operating process of step (4) are as follows:
(4.1) it is added in the high molecular system of Gao Hangu anion aqueous polyurethane prepared to step (3) remaining
Portion of diluent stirs and is cooled to 50 DEG C or less；
(4.2) neutralizer is added, and maintenance system temperature is 40~50 DEG C, stirs 15~20min；
(4.3) into mulser be added 20~35 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in the reactor of process (4.2) is added to process (4.3)
Mulser in, later maintain stirring 40~60min；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion is made.
In method of the present invention, in used raw material, polymerized monomer includes polyester-diol, diisocyanate
Ester, chain extender (i.e. nonionic chain extender and anion chain extender) and end-capping reagent；Viscosity modifier is polyethers chain extender；Adjuvant
Including chain extender, neutralizer and diluent in polymerization catalyst, bath.
In a particular embodiment, the polyester-diol is moisture content not higher than 2 ‰ and molecular weight is 1000~2000
Adipic acid/1,4- butanediol copolymer glycols, molecular weight be 2000~3000 adipic acid/diglycol copolymer glycols and
One or both of adipic acid/1,4- butanediol/diglycol copolymer glycols that molecular weight is 1500~2500 mix
Close object.As specific example, the polyester-diol is moisture content not higher than 2 ‰ and molecular weight is 2500 adipic acid/Isosorbide-5-Nitrae-
Butanediol/diglycol copolymer glycols, moisture content not higher than 2 ‰ and molecular weight be 1500 adipic acid/1,4- butanediol
Copolymer glycols or moisture content are not higher than 2 ‰ and adipic acid/diglycol copolymer glycols that molecular weight is 2000.
In a particular embodiment, the diisocyanate is two isocyanide of toluene di-isocyanate(TDI) and/or isophorone
Acid esters.
In a particular embodiment, the nonionic chain extender is 1,4-butanediol and/or neopentyl glycol.
In a particular embodiment, the anion chain extender is dihydromethyl propionic acid and/or dimethylolpropionic acid.
In method of the present invention, the end-capping reagent is gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-
At least one of gamma-aminopropyl-triethoxy-silane and γ-aminopropyltriethoxy diethoxy silane.In the present invention, it uses
Multifunctional silane coupling agent carries out active termination to polyurethane, solves the problems, such as that weak anionic macromolecule filming is poor；
Simultaneously as the molecular weight of end-cap product is smaller, it is also beneficial to obtain the lesser Gao Hangu lotion of viscosity.
In method of the present invention, the viscosity modifier selects polyethers chain extender.In a particular embodiment,
The linear polyethylene second that the polyethers chain extender is the polyethylene glycol that molecular weight is 200~600 and molecular weight is 1000~1500
The mixture of glycol methyl ether.In the present invention, smaller using molecular weight and functional expansion containing polyether lateral chain or polyether backbone
Chain agent can introduce a small amount of polyethers short chain as viscosity modifier into polyurethane side chain and skeleton structure, be equipped with substep ladder
Secondary chain extension can be effectively controlled the high molecular hydrophilic-structure distribution of product, facilitate the lotion for obtaining low viscosity.
In a specific embodiment of the invention, the polyethylene glycol can be polyethylene glycol, the molecule that molecular weight is 600
The polyethylene glycol that the polyethylene glycol or molecular weight that amount is 400 are 200.
In a specific embodiment of the invention, it is 1200 that the linear polyethylene ethylene glycol monomethyl ether, which can be molecular weight,
Linear polyethylene ethylene glycol monomethyl ether.
In method of the present invention, the polymerization catalyst can be the conventional selection of this field.Specific real
It applies in mode, the polymerization catalyst is stannous octoate and/or dibutyl tin dilaurate.
In method of the present invention, chain extender is ethylenediamine and/or making methylpentamethylenediamine diamine in the bath.In the present invention
In, using diamines in water to polyurethane terminal isocyanate groups reserved on a small quantity bathe in chain extension, can effectively avoid and reacted
The high viscosity phenomenon of journey.
In a specific embodiment of the invention, the neutralizer is triethylamine.
In a specific embodiment of the invention, the diluent be acetone, methyl ethyl ketone and ethyl pyrrolidone in extremely
Few one kind.In the present invention, the diluent is added in two steps, and a part is added in the chain extension process of step (2), remaining
Part is added in the emulsion process of step (4).In step (2) and step (4), the dosage of the diluent to polymerize
Reaction and emulsion process can be normally carried out.In more preferably embodiment, the amount for the diluent being added in step (2)
Amount no more than 80 weight % of the total dosage of diluent, preferably 60-80 weight %, the middle diluent being added of step (4) is dilute
Release the 20-40 weight % of the total dosage of agent.
In a specific embodiment of the invention, water used in step (4) is total hardness less than or equal to 50ppmCaO's
Soft water specifically, such as can be the soft water of 30-50ppmCaO.
In method of the present invention, the molfraction of step (1) dosage of each component into (4) are as follows: diisocyanate
25, polyester-diol 8~10, nonionic chain extender 6~8, anion chain extender 2~5, end-capping reagent 2~5, viscosity modifier 0.5~
0.9, wherein the sum of molfraction of polyester-diol, nonionic chain extender, anion chain extender and viscosity modifier is 18~22,
The molfraction of chain extender is (25- polyester-diol molfraction-nonionic chain extender molfraction-anion chain extension in bath
Agent molfraction-viscosity modifier that number-end-capping reagent molfraction × 0.5) × (0.3~1.2)；In the viscosity-adjusting agent
In agent, linear polyethylene ethylene glycol that polyethylene glycol that the molecular weight is 200~600 and the molecular weight are 1000~1500
The ratio between mole of methyl ether is 0.3~1.5:1, preferably 0.5~1:1.
In method of the present invention, with diisocyanate, polyester-diol, nonionic chain extender, anion chain extender
Total dosage (i.e. the total amount of polymerized monomer) with end-capping reagent is 100 parts by weight meters, and the dosage of the polymerization catalyst can be
0.04~0.06 parts by weight.
In method of the present invention, the dosage of the neutralizer can be the 0.9 of the anion chain extender weight
~1.2 times.
In method of the present invention, it is preferable that the dosage of water and the diluent makes the Gao Hangu of preparation
The solid content of anion aqueous polyurethane lotion is 50~55%.
The present invention also provides a kind of Gao Hangu anion aqueous polyurethane lotions, wherein the Gao Hangu anionic water
Property polyaminoester emulsion is made by method of the present invention.The solid content of the Gao Hangu anion aqueous polyurethane lotion can be with
It is 50~55%.The viscosity of the Gao Hangu anion aqueous polyurethane lotion can be for according to 2008/10503 method of AFAM
The delivery time measured under conditions of 23 DEG C, 4mm glasss was less than 100 seconds.
The present invention will be described in detail by way of examples below, but protection scope of the present invention is not limited to that.
Various raw materials and its dosage used in following example 1-3 are as shown in table 1 below.
Table 1
Embodiment 1
(1) pre-polymerization
(1.1) polyester-diol is put into reactor, is warming up to 70 DEG C；
(1.2) it puts into diisocyanate and maintains to stir, control temperature of reaction system is 80 DEG C, maintains to be stirred to react
20min；
(1.3) maintaining temperature of reaction system is 80 DEG C, and polymerization catalyst is at the uniform velocity put into 20min；
(1.4) heating up and controlling temperature of reaction system is 85 DEG C, insulation reaction 90min, is made high containing solid anion aqueous
Base polyurethane prepolymer for use as.
(2) chain extension
(2.1) reaction system of step (1.4) is cooled to 75 DEG C；
(2.2) viscosity modifier, anion chain extender are uniformly added into 15min, maintaining reaction temperature is 75 DEG C；
(2.3) control reaction temperature is 80 DEG C and continues to be stirred to react 20min, is cooled to 77 DEG C later and continues stirring instead
Answer 85min；
(2.4) cooling down and controlling reaction temperature is 65 DEG C, and nonionic chain extender is added and continues to be stirred to react 90min, phase
Between several times in due course addition be no more than total amount 80% diluent, to control the viscosity of reaction system, be made Gao Hangu anion
Aqueous polyurethane intermediate.
(3) it blocks
(3.1) temperature of reaction system of step (2.4) is reduced to 55 DEG C；
(3.2) end-capping reagent is uniformly added into 20min, maintaining temperature later is 55 DEG C, is stirred to react 50min, and height is made
Containing solid anion aqueous polyurethane macromolecule.
(4) it emulsifies
(4.1) remaining diluent is added to the reaction system of step (3.2), stirs and is cooled to 40 DEG C；
(4.2) neutralizer is added, and maintenance system temperature is 40 DEG C, stirs 15min；
(4.3) into mulser be added 20 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in (4.2) reactor is added in (4.3) mulser
In water, stirring 60min is maintained later；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion A1 is made.
The product purpose usage of the Gao Hangu anion aqueous polyurethane product emulsion A1: all kinds of weavings be can be widely used for
The elastic gum paste paint stamp of product and covering with paint processing, are particularly suitable for knitted textile product；Emulsion viscosity is small, it is solid high, dry to contain
Dry speed is moderate；The elastic foot of product glue film, feel smooth, flexible, water resistance are good.
The product of Gao Hangu anion aqueous polyurethane product emulsion A1 stores: finished product must be sealed at shady and cool, drying and be protected
It deposits.
Embodiment 2
(1) pre-polymerization
(1.1) polyester-diol is put into reactor, is warming up to 75 DEG C；
(1.2) it puts into diisocyanate and maintains to stir, control temperature of reaction system is 80 DEG C, maintains to be stirred to react
25min；
(1.3) maintaining temperature of reaction system is 80 DEG C, and polymerization catalyst is at the uniform velocity put into 15min；
(1.4) heating up and controlling temperature of reaction system is 85 DEG C, insulation reaction 90min, is made high containing solid anion aqueous
Base polyurethane prepolymer for use as.
(2) chain extension
(2.1) reaction system of step (1.4) is cooled to 80 DEG C；
(2.2) viscosity modifier, anion chain extender are uniformly added into 15min, maintaining reaction temperature is 80 DEG C；
(2.3) control reaction temperature is 85 DEG C and continues to be stirred to react 30min, is cooled to 80 DEG C later and continues stirring instead
Answer 90min；
(2.4) cooling down and controlling reaction temperature is 70 DEG C, and nonionic chain extender is added and continues to be stirred to react 90min, phase
Between several times in due course addition be no more than total amount 80% diluent, to control the viscosity of reaction system, be made Gao Hangu anion
Aqueous polyurethane intermediate.
(3) it blocks
(3.1) temperature of reaction system of step (2.4) is reduced to 60 DEG C；
(3.2) end-capping reagent is uniformly added into 15min, maintaining temperature later is 60 DEG C, is stirred to react 60min, and height is made
Containing solid anion aqueous polyurethane macromolecule.
(4) it emulsifies
(4.1) remaining diluent is added to the reaction system of step (3.2), stirs and is cooled to 45 DEG C；
(4.2) neutralizer is added, and maintenance system temperature is 45 DEG C, stirs 15min；
(4.3) into mulser be added 25 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in (4.2) reactor is added in (4.3) mulser
In water, stirring 45min is maintained later；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion A2 is made.
The product purpose usage of the Gao Hangu anion aqueous polyurethane product emulsion A2: all kinds of weavings be can be widely used for
The elastic gum paste paint stamp of product and covering with paint processing, are particularly suitable for knitted textile product；Emulsion viscosity is small, it is solid high, dry to contain
Dry speed is moderate；The elastic foot of product glue film, feel smooth, flexible, water resistance are good.
The product of the Gao Hangu anion aqueous polyurethane product emulsion A2 stores: finished product must be close at shady and cool, drying
Envelope saves.
Embodiment 3
(1) pre-polymerization
(1.1) polyester-diol is put into reactor, is warming up to 80 DEG C；
(1.2) it puts into diisocyanate and maintains to stir, control temperature of reaction system is 85 DEG C, maintains to be stirred to react
20min；
(1.3) maintaining temperature of reaction system is 85 DEG C, and polymerization catalyst is at the uniform velocity put into 15min；
(1.4) heating up and controlling temperature of reaction system is 90 DEG C, insulation reaction 100min, is made high containing solid anion aqueous
Base polyurethane prepolymer for use as.
(2) chain extension
(2.1) reaction system of step (1.4) is cooled to 85 DEG C；
(2.2) viscosity modifier, anion chain extender are uniformly added into 20min, maintaining reaction temperature is 85 DEG C；
(2.3) control reaction temperature is 90 DEG C and continues to be stirred to react 35min, is cooled to 83 DEG C later and continues stirring instead
Answer 80min；
(2.4) cooling down and controlling reaction temperature is 72 DEG C, and nonionic chain extender is added and continues to be stirred to react 100min, phase
Between several times in due course addition be no more than total amount 80% diluent, to control the viscosity of reaction system, be made Gao Hangu anion
Aqueous polyurethane intermediate.
(3) it blocks
(3.1) temperature of reaction system of step (2.4) is reduced to 62 DEG C；
(3.2) end-capping reagent is uniformly added into 15min, maintaining temperature later is 62 DEG C, is stirred to react 60min, and height is made
Containing solid anion aqueous polyurethane macromolecule.
(4) it emulsifies
(4.1) remaining diluent is added to the reaction system of step (3.2), stirs and is cooled to 45 DEG C；
(4.2) neutralizer is added, and maintenance system temperature is 45 DEG C, stirs 20min；
(4.3) into mulser be added 30 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in (4.2) reactor is added in (4.3) mulser
In water, stirring 50min is maintained later；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion A3 is made.
The product purpose usage of the Gao Hangu anion aqueous polyurethane product emulsion A3: all kinds of weavings be can be widely used for
The elastic gum paste paint stamp of product and covering with paint processing, are particularly suitable for knitted textile product；Emulsion viscosity is small, it is solid high, dry to contain
Dry speed is moderate；The elastic foot of product glue film, feel smooth, flexible, water resistance are good.
The product of the Gao Hangu anion aqueous polyurethane product emulsion A3 stores: finished product must be close at shady and cool, drying
Envelope saves.
Comparative example 1
Anion aqueous polyurethane lotion is prepared according to the method for embodiment 1, the difference is that viscosity modifier used is only
The linear polyethylene ethylene glycol monomethyl ether for being 1200 for molecular weight, specifically, with the molecular weight of same molar be 1200 it is linear
It is 600 polyethylene glycol that polyethylene glycol methyl ether, which replaces molecular weight, so that anion aqueous polyurethane product emulsion D1 be made.
The product purpose usage of the anion aqueous polyurethane product emulsion D1: all kinds of textile products be can be widely used for
It covers with paint, lacquer, colour wash, etc. processing and surface is modified (such as anti-fluffing and anti-pilling)；Emulsion viscosity is smaller, containing consolidating, higher, rate of drying is slower；Product is hydrophilic
Property is preferable, but extensibility is poor, and water resistance is general.
Comparative example 2
Anion aqueous polyurethane lotion is prepared according to the method for embodiment 1, the difference is that chain extender in balneation is not added
Making methylpentamethylenediamine diamine, so that anion aqueous polyurethane product emulsion D2 be made.
The product purpose usage of the anion aqueous polyurethane product emulsion D1: all kinds of textile products be can be widely used for
Cover with paint, lacquer, colour wash, etc. processing and fabric ply adhesion；Emulsion viscosity is higher, containing it is solid it is lower, rate of drying is very fast, be not suitable for screen printing；It produces
Object glue film hydrophily is general, extensibility is poor, rigidity is obvious, and water resistance is preferable.
Test case
(1) solid content of polyaminoester emulsion product A1-A3 and D1-D2 is detected according to GB/T 2793-1995 method；
(2) viscosity of polyaminoester emulsion product A1-A3 and D1-D2 is detected according to 2008/10503 method of AFAM.
Testing result is as shown in table 2 below.
Table 2
It can be seen that the anion aqueous polyurethane lotion using method of the present invention preparation by the result of table 2
Product solid content with higher, and viscosity is smaller.
The foregoing is merely preferred embodiments of the invention, actually each specific raw material cited by the present invention and each original
Bound, the section value of the bound of material, section value and technological parameter (such as temperature, time) can realize this hair
It is bright, embodiment numerous to list herein.
Therefore, above embodiments are not intended to limit the invention, and those skilled in the art is in technical solution of the present invention model
The usual variations and alternatives for enclosing interior progress should be all included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of Gao Hangu anion aqueous polyurethane lotion, which is characterized in that method includes the following steps:
(1) pre-polymerization: polyester-diol and diisocyanate, polymerization catalyst are subjected to prepolymerization reaction, Gao Hangu anionic water is made
Property base polyurethane prepolymer for use as；
(2) chain extension: by the Gao Hangu anion aqueous polyurethane performed polymer and chain extender, viscosity modifier, portion of diluent
Gao Hangu anion aqueous polyurethane intermediate is made, wherein the chain extender includes nonionic chain extender and anion in reaction
Chain extender；
(3) it blocks: by the Gao Hangu anion aqueous polyurethane intermediate and blocking agent reaction, Gao Hangu anionic water is made
Property polyurethane high molecule；
(4) it emulsifies: by chain extension in the Gao Hangu anion aqueous polyurethane macromolecule, neutralizer, remainder diluent, bath
Agent, water are mixed and are emulsified, and Gao Hangu anion aqueous polyurethane lotion is made；
Wherein, the molfraction of dosage of each component are as follows: diisocyanate 25, polyester-diol 8~10, nonionic chain extender 6~8,
Anion chain extender 2~5, end-capping reagent 2~5, viscosity modifier 0.5~0.9, wherein polyester-diol, nonionic chain extender, yin from
The sum of molfraction of sub- chain extender and viscosity modifier is 18~22, and the molfraction of chain extender is (25- polyester two in bath
Alcohol molfraction-nonionic chain extender molfraction-anion chain extender molfraction-viscosity modifier that number-envelope
Hold agent molfraction × 0.5) × (0.3~1.2)；
With total dosage of diisocyanate, polyester-diol, nonionic chain extender, anion chain extender and end-capping reagent for 100 weight
Part meter, the dosage of the polymerization catalyst are 0.04~0.06 parts by weight；
The dosage of the neutralizer is 0.9~1.2 times of the anion chain extender weight；
The linear poly- second that the viscosity modifier is the polyethylene glycol that molecular weight is 200~600 and molecular weight is 1000~1500
The mixture of allyl diglycol methyl ether, and the molecular weight be 200~600 polyethylene glycol and the molecular weight be 1000~1500
Linear polyethylene ethylene glycol monomethyl ether the ratio between mole be 0.3~1.5:1, preferably 0.5~1:1；
The end-capping reagent is gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane and γ-
At least one of aminopropyltriethoxy diethoxy silane；
Chain extender is ethylenediamine and/or making methylpentamethylenediamine diamine in the bath.
2. the method according to claim 1, wherein the operating process of step (1) are as follows:
(1.1) polyester-diol is put into reactor, is warming up to 70~80 DEG C；
(1.2) it putting into and diisocyanate and maintains to stir, control temperature of reaction system is 75~85 DEG C, maintenance is stirred to react 15~
30min；
(1.3) maintaining temperature of reaction system is 75~85 DEG C, and polymerization catalyst is at the uniform velocity put into 15~20min；
(1.4) heating up and controlling temperature of reaction system is 80~90 DEG C, 80~100min of insulation reaction, and Gao Hangu anion is made
Waterborne Polyurethane Prepolymer.
3. the method according to claim 1, wherein the operating process of step (2) are as follows:
(2.1) system of the Gao Hangu anion aqueous polyurethane performed polymer of step (1) preparation is cooled to 75~85 DEG C；
(2.2) viscosity modifier, anion chain extender are uniformly added into 10~20min, maintaining reaction temperature is 75~85 DEG C；
(2.3) control reaction temperature is 80~90 DEG C and to continue to be stirred to react 20~40min, be cooled to later 75~85 DEG C and after
It is continuous to be stirred to react 80~100min；
(2.4) cooling down and controlling reaction temperature is 65~75 DEG C, be added nonionic chain extender and continuing be stirred to react 80~
100min, during being stirred to react, addition is no more than the diluent of 80 weight % of total amount several times, to control reaction system
Viscosity, be made Gao Hangu anion aqueous polyurethane intermediate.
4. the method according to claim 1, wherein the operating process of step (3) are as follows:
(3.1) system of the Gao Hangu anion aqueous polyurethane intermediate of step (2) preparation is cooled to 55~65 DEG C；
(3.2) end-capping reagent is uniformly added into 10~20min, maintaining temperature later is 55~65 DEG C, it is stirred to react 50~
Gao Hangu anion aqueous polyurethane macromolecule is made in 70min.
5. the method according to claim 1, wherein the operating process of step (4) are as follows:
(4.1) remainder is added in the high molecular system of Gao Hangu anion aqueous polyurethane prepared to step (3)
Diluent stirs and is cooled to 50 DEG C or less；
(4.2) neutralizer is added, and maintenance system temperature is 40~50 DEG C, stirs 15~20min；
(4.3) into mulser be added 20~35 DEG C water and bath in chain extender, stirring and dissolving；
(4.4) mulser speed of agitator is improved, the reactant in the reactor of process (4.2) is added to the cream of process (4.3)
In change machine, 40~60min of stirring is maintained later；
(4.5) it stands, deaeration, Gao Hangu anion aqueous polyurethane product emulsion is made.
6. method described in any one of -5 according to claim 1, which is characterized in that the polyester-diol is that moisture content is not high
In 2 ‰ and molecular weight be 1000~2000 adipic acid/1,4- butanediol copolymer glycols, molecular weight be 2000~3000 oneself two
Adipic acid/1,4- butanediol/diglycol that acid/diglycol copolymer glycols and molecular weight are 1500~2500 is total
The mixture of one or both of polyglycols；
Preferably, the diisocyanate is toluene di-isocyanate(TDI) and/or isophorone diisocyanate；
Preferably, the polymerization catalyst is stannous octoate and/or dibutyl tin dilaurate.
7. method described in any one of -5 according to claim 1, which is characterized in that the nonionic chain extender is Isosorbide-5-Nitrae-fourth
Glycol and/or neopentyl glycol；
Preferably, the anion chain extender is dihydromethyl propionic acid and/or dimethylolpropionic acid；
Preferably, the diluent is at least one of acetone, methyl ethyl ketone and ethyl pyrrolidone.
8. method described in any one of -5 according to claim 1, which is characterized in that the neutralizer is triethylamine；
Preferably, water used in step (4) is the soft water that total hardness is less than or equal to 50ppmCaO.
9. method described in any one of -5 according to claim 1, which is characterized in that the dosage of water and the diluent makes
The solid content of the Gao Hangu anion aqueous polyurethane lotion of preparation is 50~55%.
10. a kind of Gao Hangu anion aqueous polyurethane lotion, which is characterized in that the Gao Hangu anion aqueous polyurethane cream
Liquid method as described in any one of claim 1-9 is made；
Preferably, the solid content of the Gao Hangu anion aqueous polyurethane lotion is 50~55%；
Preferably, the viscosity of the Gao Hangu anion aqueous polyurethane lotion is according to 2008/10503 method of AFAM 23
DEG C, delivery time for measuring under conditions of 4mm glasss is less than 100 seconds.
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