CN106590394A - Process of preparing waterborne polyurethane optical coating through continuous method - Google Patents
Process of preparing waterborne polyurethane optical coating through continuous method Download PDFInfo
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- CN106590394A CN106590394A CN201611052365.4A CN201611052365A CN106590394A CN 106590394 A CN106590394 A CN 106590394A CN 201611052365 A CN201611052365 A CN 201611052365A CN 106590394 A CN106590394 A CN 106590394A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a process of preparing a waterborne polyurethane optical coating through a continuous method. The process includes the steps of: (1) continuously feeding diisocyanate, an organic metal catalyst and a hydrophilic chain extender/polytetrahydrofuran ether glycol solution into a first pre-polymerization kettle to perform first-stage polymerization, and then feeding the components into a second pre-polymerization kettle to perform second-stage polymerization; (2) continuously feeding the second-stage polymerized material and a tertiary amine neutralizer into a first static mixer to perform neutralization to generate a waterborne polyurethane prepolymer; (3) feeding the prepolymer into a first high-speed shear mixing emulsifier, so that the prepolymer is emulsified in a water solution containing a sulfonate chain extender and meanwhile is subjected to a chain extension reaction, and feeding the prepolymer into a second high-speed shear mixing emulsifier, continuously adding a hydrazine hydrate after-chain extender dropwise to prepare a waterborne polyurethane emulsion; and 4) continuously mixing the waterborne polyurethane emulsion and deionized water in a second static mixer and feeding the mixture into a paint blending kettle to mix the mixture with additive pigment slurry uniformly. Compared with the prior art, the optical coating is simple in process, has good stability and is high-effective and economical.
Description
Technical field
The present invention relates to a kind of preparation technology of polyurethane coating, and in particular to a kind of continuity method prepares aqueous polyurethane light
The technique for learning coating.
Background technology
Optical coating is coated on ground can make surface show different optical characteristics, such as delustring, anti-dazzle, anti-reflective
Penetrate with high reflection etc..Used as the new coating that a class is emerging, which can be widely used in car industry, hospitality industry, army's industry
In field.
Aqueous polyurethane optical coating is produced by film-forming resin body completely because of its environmental protection and optical characteristics, in recent years in state
Inside and outside coating industry gets most of the attention.Since end of the sixties in last century industrialization, aqueous polyurethane development is extremely rapid, but its life
Up to the present production. art also only has batch process production and semi-continuous process to produce.So-called batch process production technology is to gather aqueouss
Urethane prepolymer is put to be carried out in a kettle., and neutralizes and dispersion, then realize in Scattered Kettle；In the technique synthesis, work as employing
When cheap aromatic diisocyanate is as raw material, reactivity is too big, and the time of staying is long, and being become with diamidogen chain extension can not
Control, generally requires very violent mixing power and goes dispersion so as to reach the shorter time of staying, and this wastes energy in the industrial production,
And it is higher to equipment requirements, product is also unstable.So-called semi-continuous process production technology is adopted and between batch process identical
Have a rest prepolymerization process, disperseed using continuous disperser thereafter.No matter batch process or semi-continuous process production technology, which is main
Deficiency is long the production cycle, and production automation degree is low and utilization rate of equipment and installations is low.
The companies such as Abroad in Recent Years part major company such as Dow, Mobay and Bayer have started to study the poly- ammonia of aqueouss for adopting
Ester continuity method preparation technology [Continuous Process for Synthesis of Aqueous Polyurethane Dispersions, Ye Qingxuan, polyurethane industrial, 20 (2), 2005,1-5],
Its Technology is：React prepared pre- in stirred tank first by polyhydric alcohol, containing hydrophilic group material and excess isocyanate
Polymers.Then continuously neutralize prepolymer and which is continuously scattered in the water containing chain extender, dispersions of polyurethanes is obtained.By
The addition of hydrophilic chain extender dihydromethyl propionic acid when synthetic prepolymer, the strong hydrogen bonding formability of its hydroxy-acid group cause pre-polymerization
Thing viscosity is very high and be difficult to control to, therefore it is continuous mode that these techniques are only neutralized with chain extension part, so strictly speaking, these systems
Back-up prose style free from parallelism technique is not also completely continuous processing.
The content of the invention
The purpose of the present invention is to propose to one kind that a kind of environmental protection and optical characteristics are produced by film-forming resin body completely is continuous
Method prepares the technique of aqueous polyurethane optical coating, obtained coating have optical characteristics substantially, solid content is higher, do not contain
The characteristics such as machine solvent, excellent storage stability；Preparation technology can energy efficient, improve production efficiency, and product quality is stable, is suitable to
Fairly large production.
During synthetic prepolymer of the present invention, overcome due to adding hydrophilic chain extender 2,2- dihydromethyl propionic acids, its carboxylic acid group
The strong hydrogen bonding of group is formed causes the very high and unmanageable problem of prepolymer viscosity；The present invention is based on hydrophilic chain extension in prepolymerization reaction
The difference of the hydroxyl activity of agent and PTMG, is to obtain hydrophilic chain extender to be distributed in prepolymer molecule chain
It is even, and to avoid being introduced into for hydrophilic chain extender from making system viscosity in prepolymer building-up process too high, optimization design two benches
Prepolymerization technology.The present invention is continuous technology method with chain extension using pre-polymerization, neutralization, is led to by changing reaction mass
Enter temperature and the time of staying, the stir speed (S.S.) of chain extending reaction of speed, pre-polymerization and neutralization reaction etc., realize good emulsion stability,
Particle size analysis size and its be distributed it is controllable, obtained coating have optical characteristics substantially, solid content it is higher, without organic molten
The characteristics such as agent, excellent storage stability.
The present invention is adopted the following technical scheme that to achieve these goals：
A kind of continuity method prepares the technique of aqueous polyurethane optical coating, comprises the following steps：
(1) by diisocyanate, hydrophilic chain extender/PTMG solution, organo-metallic catalyst respectively with
15～20 kgs/hour, 30～36 kgs/hour, 2～20 Grams Per Hour speed are continuously passed through or instill the first prepolymerization kettle and carry out
One-step polymerization：The time of staying is 1.0～1.5 hours, and reaction temperature is controlled at 55～65 DEG C；Then it is passed through the second prepolymerization kettle again to enter
Row two-stage nitration is polymerized：The time of staying is 2.0～2.5 hours, and reaction temperature is controlled at 75～85 DEG C；Hydrophilic chain extender and poly- tetrahydrochysene furan
Mutter the mass ratio 1 of ether glycol：20～25；
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer uncle with tertiary amines nertralizer
Amine nertralizer, is passed through speed for 0.8～1.2 kg/hour, after neutralizing into salt 0.15～0.25 hour, is cooled to room temperature, i.e.,
Obtain waterborne polyurethane prepolymer；
(3) waterborne polyurethane prepolymer is passed through the first high speed shear mixing emulsifier, containing sulfonate type chain extender
There is chain extending reaction in aqueous solution while emulsifying：Sulfonate type chain extender (mass concentration 0.5～6%) aqueous solution is passed through speed
Spend for 65～75 kgs/hour, chain extending reaction 0.25～0.35 hour, stir speed (S.S.) are controlled in 1400rpm～3200rpm；So
After send into the second high speed shear mixing emulsifier, continuous Deca hydrazine hydrate rear chain extender reaction obtains aqueous polyurethane emulsion：Water
It is 1～2 kg/hour to close hydrazine rate of addition, rear chain extending reaction 0.15～0.25 hour, stir speed (S.S.) control 600rpm～
1000rpm；
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer with deionized water, it is solid to adjust emulsion
20～45%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed to content；Finally, will allotment
Good aqueous polyurethane emulsion is passed through paint mixing kettle and is mixed with adjuvant pigments slurry, obtains aqueous polyurethane optical coating.
Further to realize the object of the invention, it is preferable that step (1) diisocyanate is isophorone diisocyanate
Ester and/or XDI.
Preferably, the hydrophilic chain extender described in step (1) is 2,2- dihydromethyl propionic acids and/or 2,2- dihydroxymethyl fourth
Acid.
Preferably, the PTMG molecular weight described in step (1) is 1000g/mol.
Preferably, the organo-metallic catalyst described in step (1) is in isooctyl acid bismuth and dibutyl tin laurate
Kind.
Preferably, the tertiary amines nertralizer described in step (2) is triethylamine and/or tripropyl amine (TPA).
Preferably, the sulfonate type chain extender described in step (3) is the third sulphur of ethylenediamine base ethyl sulfonic acid sodium and/or ethylenediamine base
Sour sodium.
Preferably, the emulsion feed speed of step (4) second static mixer is to prepare aqueous polyurethane emulsion institute
There is the admission velocity sum of material.
Preferably, adjuvant pigments slurry include Bi Ke chemical companies of Germany BYK-019 and BYK-141 defoamer,
BYK-333 and BYK-346 levelling agents, the Borchi Gel LW44 thickening agents of OMG companies of the U.S. and U.S. Momentive are high
CoatOSil1770 firming agent of new material company etc..
Compared with prior art, the invention has the advantages that：
1st, the present invention based on hydrophilic chain extender in prepolymerization reaction and the difference of the hydroxyl activity of PTMG is
Obtain hydrophilic chain extender to be evenly distributed in prepolymer molecule chain, and to avoid the introducing of hydrophilic chain extender from synthesizing prepolymer
During system viscosity it is too high, optimization design two benches prepolymerization technologies；It is when avoiding synthetic prepolymer, hydrophilic due to adding
Chain extender 2,2- dihydromethyl propionic acids, the strong hydrogen bonding of its hydroxy-acid group are formed and cause that prepolymer viscosity is very high and unmanageable to ask
Topic；
2nd, the inventive method by change reaction mass be passed through speed, pre-polymerization and neutralization reaction temperature and the time of staying,
Stir speed (S.S.) of chain extending reaction etc., realizes good emulsion stability, particle size analysis size and its is distributed controllable, obtained coating tool
Have optical characteristics substantially, solid content it is higher, without characteristics such as organic solvent, excellent storage stabilities.
3rd, in the method for the present invention, prepolymerization and its neutralization chain extension adopt double kettles and the in-line company of polyhybird (emulsifying) device
Continuous preparation technology, N-process and dispersive process are carried out in continuous mode, can energy efficient, improve production efficiency, and produce
Quality is stable, is suitable to fairly large production.
4th, it is of the invention because its pre- collecting process, N-process and dispersive process are carried out in continuous mode, in synthesis
It is convenient to add other dispersion liquids to be blended, in final finished, add various auxiliary agents to be also easier control, therefore product quality is stable,
Production economy is efficient.
Description of the drawings
Fig. 1 is the schematic flow sheet of the technique that continuity method of the present invention prepares aqueous polyurethane optical coating.
Illustrate in figure：First prepolymerization kettle 1, the second prepolymerization kettle 2, the first static mixer 3, the first high speed shear mixing and emulsifying
Device 4, the second high speed shear mixing emulsifier 5, the second static mixer 6, the first paint mixing kettle 7, the second paint mixing kettle 8, the 3rd paint
Kettle 9.
Specific embodiment
The present invention is further illustrated below by the specific descriptions to the embodiment of the present invention, it should be noted that implementing
Example does not constitute the restriction to the claimed scope of the invention.Embodiment result is summarized in table 1.
In embodiment, involved method of testing is described as follows：
1) solid content：Determine according to GB/T1725-1979 solids coatings algoscopy.
2) apply membrane preparation method：Method is typically prepared according to GB/T1727-1992 paint films, the aqueous polyurethane optics that will be prepared
The method of coating roller coating coats the glass plate of cleaning, and film thickness is (35 ± 5) μm, is then toasted in 110 DEG C of baking oven
1min, after being completely dried, is cooled to room temperature standby.
3) film light transmittance：Film is tested with U.S.'s Agilent companies Cary60 type ultraviolet-uisible spectrophotometers,
Sweep limitss are 300nm～700nm, and scanning speed is 600nm/min.
4) coating film gloss degree：By ISO/2813 standards, determined using the 500MC types gloss meter of German Erichsen companies and applied
60 ° of glossiness of film.
As shown in figure 1, a kind of continuity method prepares the flow process of the technique of aqueous polyurethane optical coating, including the first prepolymerization kettle
1st, the second prepolymerization kettle 2, the first static mixer 3, the first high speed shear mixing emulsifier 4, the second high speed shear mixing emulsifier
5th, the second static mixer 6, the first paint mixing kettle 7, the second paint mixing kettle 8, the 3rd paint mixing kettle 9；First prepolymerization kettle 1, the second prepolymerization kettle
2nd, the first static mixer 3, the first high speed shear mixing emulsifier 4, the second high speed shear mixing emulsifier 5 and second are static mixed
Clutch 6 is sequentially communicated；Second static mixer 6 is connected with the first paint mixing kettle 7, the second paint mixing kettle 8, the 3rd paint mixing kettle 9 respectively；The
One prepolymerization kettle 1 is fed with diisocyanate, hydrophilic chain extender/PTMG solution and organo-metallic catalyst respectively
Device connects；First static mixer 3 is connected with agent feeding device with tertiary amines；First high speed shear mixing emulsifier 4 with
Sulfonate type chain extender and the connection of deionized water feeding device；Second high speed shear mixing emulsifier 5 and hydrazine hydrate charging dress
Put connection；Deionized water feeding device is also adjusted with the second high speed shear mixing emulsifier 5 and the first paint mixing kettle 7, second respectively
Paint kettle 8, the 3rd paint mixing kettle 9 are connected；First paint mixing kettle 7 obtains antiglossing pigment；Second paint mixing kettle 8 obtains anti-dazzle optical coating；3rd
Paint mixing kettle 9 is standby.
Embodiment 1
(1) by isophorone diisocyanate, 2,2- dihydromethyl propionic acids/PTMG (mass ratio 1：24)
Solution, isooctyl acid bismuth are continuously passed through (or instillation) with 18.9 kgs/hour, 35.7 kgs/hour, 2.3 Grams Per Hour speed respectively
First prepolymerization kettle 1 carries out one-step polymerization：The time of staying is 1.0 hours, and reaction temperature is controlled at 60 DEG C；Then it is pre- that second is passed through again
Poly- kettle 2 carries out two-stage nitration polymerization：The time of staying is 2.0 hours, and reaction temperature is controlled at 80 DEG C.
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer 3, triethylamine with triethylamine
Speed is passed through for 1.1 kgs/hour, after neutralizing into salt 0.15 hour, room temperature is cooled to, is obtained final product waterborne polyurethane prepolymer.
(3) waterborne polyurethane prepolymer is passed through the first high speed shear mixing emulsifier 4, is passed through ethylenediamine base ethyl sulfonic acid sodium
(mass concentration 0.6%) aqueous solution, the speed that is passed through of ethylenediamine base ethyl sulfonic acid sodium water solution is 64 kgs/hour, chain extending reaction
0.35 hour, stir speed (S.S.) was controlled in 1400rpm；The second high speed shear mixing emulsifier 5 is then fed into, hydrazine hydrate is public with 1.8
The continuous Deca of jin/hour, rear chain extending reaction 0.15 hour, stir speed (S.S.) are controlled in 600rpm, obtain final product aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer 6 with deionized water, it is solid to adjust emulsion
30%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed to content；Finally, will be deployed
Aqueous polyurethane emulsion is passed through the first paint mixing kettle 7 and mixes (by percentage to the quality, antiglossing pigment bag with metering adjuvant pigments slurry
Include 80% aqueous polyurethane emulsion, 0.5% BYK-019 defoamer, 3% BYK-333 levelling agents, 1% Borchi
Gel LW44 thickening agents and 1.5% CoatOSil1770 firming agent, remaining as deionized water, each component summation is
100%) aqueous polyurethane antiglossing pigment, is obtained final product, 60 ° of its coating film, glossiness is 2, shows excellent extinction effect.
Embodiment 2
(1) by XDI, 2,2- dimethylolpropionic acids/PTMG (mass ratio 1：
21) solution, dibutyl tin laurate respectively with 16.0 kgs/hour, 35.9 kgs/hour, 12.5 Grams Per Hour speed it is continuous
Being passed through (or instillation) first prepolymerization kettle carries out one-step polymerization：The time of staying is 1.5 hours, and reaction temperature is controlled at 55 DEG C；Then
Being passed through the second prepolymerization kettle again carries out two-stage nitration polymerization：The time of staying is 2.0 hours, and reaction temperature is controlled at 85 DEG C.
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer with tripropyl amine (TPA), and tripropyl amine (TPA) leads to
Enter speed for 1.6 kgs/hour, after neutralizing into salt 0.25 hour, be cooled to room temperature, obtain final product waterborne polyurethane prepolymer.
(3) prepolymer is passed through the first high speed shear mixing emulsifier, ethylenediamine base ethyl sulfonic acid sodium (mass concentration 1.2%) water
The speed that is passed through of solution is 32 kgs/hour, and chain extending reaction 0.35 hour, stir speed (S.S.) are controlled in 1800rpm；It is then fed into
Two high speed shear mixing emulsifiers, hydrazine hydrate is with 1.8 kgs/hour of continuous Deca, rear chain extending reaction 0.15 hour, stir speed (S.S.)
Control obtains final product aqueous polyurethane emulsion in 800rpm.
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer with deionized water, it is solid to adjust emulsion
40%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed to content；Finally, will be deployed
Aqueous polyurethane emulsion is passed through the first paint mixing kettle 7 and mixes (by percentage to the quality, antiglossing pigment bag with metering adjuvant pigments slurry
Include 90% aqueous polyurethane emulsion, 3% BYK-141 defoamer, 3% BYK-346 levelling agents, 0.5% Borchi
Gel LW44 thickening agents and 0.5% CoatOSil1770 firming agent, remaining as deionized water, each component summation is
100%), obtain final product aqueous polyurethane antiglossing pigment.
Embodiment 3
(1) by isophorone diisocyanate, 2,2- dihydromethyl propionic acids/PTMG (mass ratio 1：24)
Solution, dibutyl tin laurate are continuously led to 18.1 kgs/hour, 34.0 kgs/hour, 17.3 Grams Per Hour speed respectively
Entering (or instillation) first prepolymerization kettle carries out one-step polymerization：The time of staying is 1.5 hours, and reaction temperature is controlled at 60 DEG C；Then again
Being passed through the second prepolymerization kettle carries out two-stage nitration polymerization：The time of staying is 2.5 hours, and reaction temperature is controlled at 80 DEG C.
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer with triethylamine, and triethylamine leads to
Enter speed for 1.0 kgs/hour, after neutralizing into salt 0.25 hour, be cooled to room temperature, obtain final product waterborne polyurethane prepolymer.
(3) prepolymer is passed through the first high speed shear mixing emulsifier, ethylenediamine base ethyl sulfonic acid sodium (mass concentration 5.1%) water
The speed that is passed through of solution is 75 kgs/hour, and chain extending reaction 0.25 hour, stir speed (S.S.) are controlled in 3000rpm；It is then fed into
Two high speed shear mixing emulsifiers, hydrazine hydrate is with 1.1 kgs/hour of continuous Deca, rear chain extending reaction 0.15 hour, stir speed (S.S.)
Control obtains final product aqueous polyurethane emulsion in 1000rpm.
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer with deionized water, it is solid to adjust emulsion
30%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed to content；Finally, will be deployed
Aqueous polyurethane emulsion is passed through the second paint mixing kettle 8 and mixes (by percentage to the quality, anti-dazzle optical coating with metering adjuvant pigments slurry
Aqueous polyurethane emulsion, 3% BYK-019 defoamer including 70%, 3% BYK-333 levelling agents, 3% Borchi
Gel LW44 thickening agents and 1.5% CoatOSil1770 firming agent, remaining as deionized water, each component summation is
100%), obtain final product the anti-dazzle optical coating of aqueous polyurethane.
Embodiment 4
(1) by XDI, 2,2- dihydromethyl propionic acids/PTMG (mass ratio 1：
22) solution, isooctyl acid bismuth are continuously passed through (or drop respectively with 15.3 kgs/hour, 33.4 kgs/hour, 6.5 Grams Per Hour speed
Entering) the first prepolymerization kettle carries out one-step polymerization：The time of staying is 1.0 hours, and reaction temperature is controlled at 65 DEG C；Then second is passed through again
Prepolymerization kettle carries out two-stage nitration polymerization：The time of staying is 2.5 hours, and reaction temperature is controlled at 75 DEG C.
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer with triethylamine, and triethylamine leads to
Enter speed for 1.0 kgs/hour, after neutralizing into salt 0.15 hour, be cooled to room temperature, obtain final product waterborne polyurethane prepolymer.
(3) prepolymer is passed through the first high speed shear mixing emulsifier, ethylenediamine base propanesulfonate (mass concentration 3.0%) water
The speed that is passed through of solution is 137 kgs/hour, and chain extending reaction 0.35 hour, stir speed (S.S.) are controlled in 2000rpm；It is then fed into
Second high speed shear mixing emulsifier, hydrazine hydrate is with 1.1 kgs/hour of continuous Deca, rear chain extending reaction 0.25 hour, stirring speed
Rate is controlled in 800rpm, obtains final product aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer with deionized water, it is solid to adjust emulsion
20%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed to content；Finally, will be deployed
Aqueous polyurethane emulsion is passed through the second paint mixing kettle 8 and mixes (by percentage to the quality, anti-dazzle optical coating with metering adjuvant pigments slurry
Aqueous polyurethane emulsion, 0.5% BYK-141 defoamer, 0.5% BYK-346 levelling agents including 80%, 3%
Borchi Gel LW44 thickening agents and 0.1% CoatOSil1770 firming agent, remaining as deionized water, each component summation
100%), to obtain final product the anti-dazzle optical coating of aqueous polyurethane.
The test result of embodiment of the present invention 1-4 is shown in Table 1.
The quantitative measurement result of 1 embodiment of the present invention aqueous polyurethane optical coating film of table
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Light transmittance (%) | 7 | 9 | 91 | 87 |
| Glossiness (60 °) | 2 | 3 | 32 | 41 |
As seen from Table 1：Embodiment 1 is respectively 2 and 3 with 60 ° of glossiness for applying example 2, close to zero diopter rank, shows excellent
Different extinction effect；The leading indicator of the Anti Glare Coatings standard of Japanese Hakawa Paper-making Co., Ltd., i.e. light transmittance >=
87% and 60 ° of glossiness be 35 ± 15, embodiment 3 and embodiment 4 are presented good anti-glare properties energy.
The test such as Erdem of Dow Chemical Company shows, in isophorone diisocyanate-prepolymer system, Carbimide.
When base mass fraction is 5%, 2,2- dihydromethyl propionic acid mass fractions only 2% have been difficult to lower disperse prepolymer solvent-free
Yu Shuizhong.The strong hydrogen bonding formability of the hydroxy-acid group of possible 2,2- dihydromethyl propionic acids is cause prepolymer viscosity high main
Reason.With 2, the 2- dihydromethyl propionic acids and 2- methyl isophthalic acids of identical molal quantity, ammediol (0.224mol/100g prepolymers),
Prepolymer is respectively synthesized under the same conditions, the former prepolymer viscosity is more much higher than the latter, almost differ 1 number at room temperature
Magnitude.It is a discovery of the invention that prepolymerization speed is too fast, hydrophilic chain extender segment skewness in polyurethane molecular structure can be made
It is even, as a result cause product property to be deteriorated.And hydrophilic chain extender, PTMG and di-isocyanate reaction are a pair
Unexpectedly strive reaction.At a lower temperature, in hydrophilic chain extender, hydroxyl activity is relatively low, and which is slower with the reaction of diisocyanate, isocyanide
The general first and PTMG (mass ratio 1 of hydrophilic chain extender and PTMG of acid esters：20～25)
Hydroxyl reaction.When system is in the condition of high temperature, the hydroxyl activity in hydrophilic chain extender strengthens, and the reaction with isocyanates adds
Hurry up.In addition, the reaction of diisocyanate and hydroxyl belongs to exothermic reaction, in course of reaction, system temperature easily soar to 80 DEG C with
On, now, the reactivity increase of hydrophilic chain extender, while difficult control of temperature, it will make hydrophilic chain extender in polyurethane
Skewness in strand, causes product property to be deteriorated.Therefore the present invention is heated up using two benches and controls prepolymerization technology, to reach
To the purpose that acquisition hydrophilic chain extender is evenly distributed in polyurethane molecular chain.Now, according to batch process prepolymerization, then two sections
The prepolymerization production cycle is longer, and capacity utilization is low.
The present invention by continuous two benches temperature rise prepolymerization, overcome general aqueous polyurethane synthetic prepolymer viscosity compared with
It is high, it is difficult to realize that quantity-produced is not enough in prepolymerisation stage.The present invention is continuous technique with chain extension using pre-polymerization, neutralization
Technical method realizes the preparation of aqueous polyurethane optical coating, and the method is continuously gathered with external major company existing aqueous polyurethane
Conjunction technology is compared, it is to avoid during addition hydrophilic chain extender dihydromethyl propionic acid, and the strong hydrogen bonding of its hydroxy-acid group is formed and causes pre-polymerization
The very high and unmanageable problem of thing viscosity, while preparation time 1-2 hours can be shortened, saves energy consumption about 20-30%.
Claims (9)
1. the technique that a kind of continuity method prepares aqueous polyurethane optical coating, it is characterised in that comprise the following steps：
(1) by diisocyanate, hydrophilic chain extender/PTMG solution, organo-metallic catalyst respectively with 15～
20 kgs/hour, 30～36 kgs/hour, 2～20 Grams Per Hour speed are continuously passed through or instill the first prepolymerization kettle carries out one section
Polymerization：The time of staying is 1.0～1.5 hours, and reaction temperature is controlled at 55～65 DEG C；Then being passed through the second prepolymerization kettle again carries out two
Duan Juhe：The time of staying is 2.0～2.5 hours, and reaction temperature is controlled at 75～85 DEG C；Hydrophilic chain extender and PTMG
The mass ratio 1 of glycol：20～25；
(2) the two-stage nitration polymer material for obtaining step (1) is continuously passed through the first static mixer tertiary amines with tertiary amines nertralizer
Nertralizer, is passed through speed for 0.8～1.2 kg/hour, after neutralizing into salt 0.15～0.25 hour, is cooled to room temperature, obtains final product water
Property polyurethane prepolymer；
(3) waterborne polyurethane prepolymer is passed through the first high speed shear mixing emulsifier, containing the water-soluble of sulfonate type chain extender
There is chain extending reaction in liquid while emulsifying：The speed that is passed through of sulfonate type chain extender (mass concentration 0.5～6%) aqueous solution is
65～75 kgs/hour, chain extending reaction 0.25～0.35 hour, stir speed (S.S.) are controlled in 1400rpm～3200rpm；Then send
Enter the second high speed shear mixing emulsifier, continuous Deca hydrazine hydrate rear chain extender reaction obtains aqueous polyurethane emulsion：Hydrazine hydrate
Rate of addition be 1～2 kg/hour, rear chain extending reaction 0.15～0.25 hour, stir speed (S.S.) control 600rpm～
1000rpm；
(4) aqueous polyurethane emulsion is continuously mixed in the second static mixer with deionized water, to adjust emulsion solid content
20～45%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；Finally, will be deployed
Aqueous polyurethane emulsion is passed through paint mixing kettle and is mixed with adjuvant pigments slurry, obtains aqueous polyurethane optical coating.
2. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly (1) described diisocyanate is isophorone diisocyanate and/or XDI.
3. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the hydrophilic chain extender described in (1) is 2,2- dihydromethyl propionic acids and/or 2,2- dimethylolpropionic acids.
4. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the PTMG molecular weight described in (1) is 1000g/mol.
5. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the organo-metallic catalyst described in (1) is the one kind in isooctyl acid bismuth and dibutyl tin laurate.
6. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the tertiary amines nertralizer described in (2) is triethylamine and/or tripropyl amine (TPA).
7. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the sulfonate type chain extender described in (3) is ethylenediamine base ethyl sulfonic acid sodium and/or ethylenediamine base propanesulfonate.
8. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Step
Suddenly the emulsion feed speed of (4) described second static mixer be prepare aqueous polyurethane emulsion all materials admission velocity it
With.
9. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Institute
Stating adjuvant pigments slurry includes BYK-019 and BYK-141 defoamer, BYK-333 the and BYK-346 levellings of Bi Ke chemical companies of Germany
Agent, the Borchi Gel LW44 thickening agents of OMG companies of the U.S. and Momentive new high-tech materials company of the U.S.
CoatOSil1770 firming agent.
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| CN114230762A (en) * | 2021-12-31 | 2022-03-25 | 黄山联固新材料科技有限公司 | Waterborne polyurethane and continuous preparation process thereof |
| CN114409553A (en) * | 2022-01-28 | 2022-04-29 | 华南理工大学 | Biquaternary ammonium salt-containing diol, preparation method thereof and application thereof in antibacterial self-extinction aqueous polyurethane coating |
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