CN106590394B - A kind of technique that continuity method prepares aqueous polyurethane optical coating - Google Patents
A kind of technique that continuity method prepares aqueous polyurethane optical coating Download PDFInfo
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- CN106590394B CN106590394B CN201611052365.4A CN201611052365A CN106590394B CN 106590394 B CN106590394 B CN 106590394B CN 201611052365 A CN201611052365 A CN 201611052365A CN 106590394 B CN106590394 B CN 106590394B
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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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- 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
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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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Abstract
The invention discloses the techniques that a kind of continuity method prepares aqueous polyurethane optical coating.The technique includes：1) diisocyanate, organo-metallic catalyst and hydrophilic chain extender/polytetrahydrofuran ether glycol solution are continuously passed through the first prepolymerization kettle and carry out one-step polymerization；It is passed through the second prepolymerization kettle again and carries out two sections of polymerizations.2) obtain two sections of polymer materials and tertiary amines neutralizer are continuously passed through the first static mixer neutralization reaction and generate waterborne polyurethane prepolymer.3) prepolymer is passed through the first high speed shear mixing emulsifier, and chain extending reaction occurs while emulsification in the aqueous solution containing sulfonate type chain extender；It is sent into the second high speed shear mixing emulsifier, the continuous hydrazine hydrate rear chain extender that is added dropwise obtains aqueous polyurethane emulsion.4) aqueous polyurethane emulsion is continuously mixed with deionized water in the second static mixer；It is passed through paint mixing kettle and starches mixing with adjuvant pigments.Compared with prior art, the present invention is with product preparation process is simple, stability is good, high-efficiency and economic feature.
Description
Technical field
The present invention relates to a kind of preparation processes 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, which is coated on ground, can make surface show different optical characteristics, such as delustring, anti-dazzle, anti-reflective
Penetrate with high reflection etc..As the new coating that one kind is emerging, car industry, hospitality industry, army's industry can be widely used in
Equal fields.
Aqueous polyurethane optical coating is because its environmental protection and optical characteristics are generated by film-forming resin ontology completely, in recent years in state
Inside and outside coating industry attracts attention.Since the end of the sixties in last century industrializes, aqueous polyurethane development is extremely rapid, but it is given birth to
Up to the present production. art also only has batch process production and semi-continuous process production.So-called batch process production technology is will be aqueous poly-
Urethane prepolymer is put to carry out in a kettle, and neutralizes and disperse, then is realized in Scattered Kettle；In technique synthesis, work as use
When cheap aromatic diisocyanate is as raw material, reactivity is too big, and the residence time is long, and being become with diamines chain extension can not
Control, generally requires very violent mixing power and goes to disperse to reach the shorter residence time, this wastes energy in the industrial production,
And it is higher to equipment requirement, product is also unstable.So-called semi-continuous process production technology is to use identical with batch process
It has a rest prepolymerization process, is disperseed using continuous disperser thereafter.No matter batch process or semi-continuous process production technology, it is main
Deficiency is that the production cycle is long, and production automation degree is low low with utilization rate of equipment and installations.
The companies such as Abroad in Recent Years part major company such as Dow, Mobay and Bayer have begun one's study the aqueous poly- ammonia of use
Ester continuity method preparation process [Continuous Process for Synthesis of Aqueous Polyurethane Dispersions, Ye Qingxuan, polyurethane industrial, 20 (2), 2005,1-5],
Its technology is：React obtained pre- in stirred tank by polyalcohol, containing hydrophilic radical substance and excess isocyanate first
Polymers.Then it continuously neutralizes prepolymer and is continuously scattered in it in water containing chain extender, dispersions of polyurethanes is made.By
The strong hydrogen bonding formability of the addition of hydrophilic chain extender dihydromethyl propionic acid when synthetic prepolymer, carboxylic acid group leads to pre-polymerization
Object viscosity is very high and uncontrollable, therefore it is continuous mode that these techniques, which are only neutralized with chain extension part, so strictly speaking, these systems
Back-up granular media technique is not also complete continuous processing.
Invention content
The one kind generated completely by film-forming resin ontology the purpose of the present invention is to propose to a kind of environmental protection and optical characteristics is continuous
Method prepares the technique of aqueous polyurethane optical coating, and obtained coating is apparent with optical characteristics, solid content is higher, does not contain
The characteristics such as solvent, excellent storage stability；Preparation process can save energy consumption, improve production efficiency, and product quality is stablized, and is suitable for
Fairly large production.
When synthetic prepolymer of the present invention, overcome since hydrophilic chain extender 2,2- dihydromethyl propionic acids, carboxylic acid group is added
The strong hydrogen bonding of group forms the problem for causing prepolymer viscosity very high and uncontrollable；The present invention is based on hydrophilic chain extensions in prepolymerization reaction
The difference of the hydroxyl activity of agent and polytetrahydrofuran ether glycol is distributed to obtain hydrophilic chain extender in prepolymer molecule chain
It is even, and to avoid being introduced into for hydrophilic chain extender from keeping system viscosity in prepolymer building-up process excessively high, optimization design two benches
Prepolymerization technology.The present invention is continuous technology method using pre-polymerization, neutralization and chain extension, logical by changing reaction mass
Enter speed, pre-polymerization and the temperature of neutralization reaction and the stir speed (S.S.) etc. of residence time, chain extending reaction, realize good emulsion stability,
Particle size analysis size and its distribution are controllable, and obtained coating is apparent with optical characteristics, solid content is higher, without organic molten
The characteristics such as agent, excellent storage stability.
The present invention adopts the following technical scheme that achieve the goals above：
A kind of continuity method prepares the technique of aqueous polyurethane optical coating, includes the following steps：
(1) by diisocyanate, hydrophilic chain extender/polytetrahydrofuran ether glycol solution, organo-metallic catalyst respectively with
15~20 kgs/hour, 30~36 kgs/hour, 2~20 Grams Per Hour speed be continuously passed through or instill the first prepolymerization kettle progress
One-step polymerization：Residence time is 1.0~1.5 hours, and reaction temperature is controlled at 55~65 DEG C；Then be passed through again the second prepolymerization kettle into
Two sections of polymerizations of row：Residence time is 2.0~2.5 hours, and reaction temperature is controlled at 75~85 DEG C；Hydrophilic chain extender and poly- tetrahydrochysene furan
It mutters the mass ratio 1 of ether glycol：20~25；The hydrophilic chain extender is 2,2- dihydromethyl propionic acids and/or 2,2- dihydroxymethyls
Butyric acid.
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer uncle with tertiary amines neutralizer
Amine, it is 0.8~1.2 kg/hour that neutralizer, which is passed through speed, after being neutralized 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, is containing sulfonate type chain extender
Chain extending reaction occurs while emulsification in aqueous solution：The sulfonate type chain extender aqueous solution of mass concentration 0.5~6% is passed through speed
Degree is 65~75 kgs/hour, and chain extending reaction 0.25~0.35 hour, stir speed (S.S.) is controlled in 1400rpm~3200rpm；So
After be sent into the second high speed shear mixing emulsifier, the continuous hydrazine hydrate chain extender reaction that is added dropwise obtains aqueous polyurethane emulsion：Hydration
Hydrazine 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 with deionized water in the second static mixer, it is solid to adjust lotion
For content 20~45%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；Finally, it will allocate
Good aqueous polyurethane emulsion is passed through paint mixing kettle and starches mixing with adjuvant pigments, obtains aqueous polyurethane optical coating.
To further realize the object of the invention, it is preferable that step (1) described diisocyanate is isophorone diisocyanate
Ester and/or benzene dimethylene diisocyanate.
Preferably, the polytetrahydrofuran ether glycol molecular weight described in step (1) is 1000g/mol.
Preferably, the organo-metallic catalyst described in step (1) is one in isooctyl acid bismuth and dibutyl tin laurate
Kind.
Preferably, the tertiary amines neutralizer 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 ethanesulfonic acid sodium and/or ethylenediamine base
Sour sodium.
Preferably, the emulsion feed speed of step (4) second static mixer is prepares aqueous polyurethane emulsion institute
There is the sum of the admission velocity of material.
Preferably, adjuvant pigments slurry include Bi Ke chemical companies of Germany BYK-019 and BYK-141 antifoaming agent,
BYK-333 and BYK-346 levelling agents, the Borchi Gel LW44 thickeners of OMG companies of the U.S. and U.S. Momentive high
CoatOSil1770 curing agent of new material company etc..
Compared with prior art, the invention has the advantages that：
1, the present invention is based on the difference of hydrophilic chain extender in prepolymerization reaction and the hydroxyl activity of polytetrahydrofuran ether glycol, it is
It obtains hydrophilic chain extender to be evenly distributed in prepolymer molecule chain, and to avoid the introducing of hydrophilic chain extender that prepolymer is made to synthesize
System viscosity is excessively high in the process, optimization design two benches prepolymerization technologies；It is hydrophilic due to being added when avoiding synthetic prepolymer
The strong hydrogen bonding formation of chain extender 2,2- dihydromethyl propionic acids, carboxylic acid group causes prepolymer viscosity is very high and uncontrollable to ask
Topic；
2, the method for the present invention by change reaction mass be passed through speed, pre-polymerization and the temperature of neutralization reaction and residence time,
The stir speed (S.S.) etc. of chain extending reaction realizes that good emulsion stability, particle size analysis size and its distribution are controllable, obtained coating tool
Have that optical characteristics is apparent, solid content is higher, without characteristics such as organic solvent, excellent storage stabilities.
3, the company of prepolymerization and its neutralization chain extension use double kettles and polyhybird (emulsification) device tandem in method of the invention
Continuous preparation process, N-process and dispersion process carry out in continuous mode, can save energy consumption, improve production efficiency, and produce
Quality is stablized, and fairly large production is suitable for.
4, of the invention because its pre- collecting process, N-process and dispersion process carry out in continuous mode, in synthesis
Facilitate and other dispersion liquids blendings are added, various auxiliary agents are added in final finished and are also easier to control, therefore product quality is stablized,
Production economy is efficient.
Description of the drawings
Fig. 1 is the flow diagram for the technique that continuity method of the present invention prepares aqueous polyurethane optical coating.
It is shown 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, third paint
Kettle 9.
Specific implementation mode
It is further illustrated the present invention below by the specific descriptions to the embodiment of the present invention, it should be noted that implement
Example does not constitute the restriction to the claimed scope of the invention.Embodiment result is summarized in table 1.
Involved test method is described as follows in embodiment：
1) solid content：It is measured according to GB/T1725-1979 solids coatings measuring methods.
2) membrane preparation method is applied：It is typically prepared method according to GB/T1727-1992 paint films, by the aqueous polyurethane optics of preparation
The method of coating roller coating is coated on clean glass plate, and film thickness is (35 ± 5) μm, is then toasted in 110 DEG C of baking oven
After being completely dried, it is spare to be cooled to room temperature by 1min.
3) film light transmittance：Film is tested with U.S.'s Agilent companies Cary60 type ultraviolet-uisible spectrophotometers,
Scanning range is 300nm~700nm, sweep speed 600nm/min.
4) coating film gloss degree：By ISO/2813 standards, is measured and applied using the 500MC type gloss meters of German Erichsen companies
60 ° of glossiness of film.
As shown in Figure 1, a kind of continuity method prepares the flow of the technique of aqueous polyurethane optical coating, including the first prepolymerization kettle
1, 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
5, the second static mixer 6, the first paint mixing kettle 7, the second paint mixing kettle 8, third paint mixing kettle 9；First prepolymerization kettle 1, 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 5 and second are static mixed
Clutch 6 is sequentially communicated；Second static mixer 6 is connected to the first paint mixing kettle 7, the second paint mixing kettle 8, third paint mixing kettle 9 respectively；The
One prepolymerization kettle 1 feeds with diisocyanate, hydrophilic chain extender/polytetrahydrofuran ether glycol solution and organo-metallic catalyst respectively
Device connects；First static mixer 3 is connect with tertiary amines with agent feeding device；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 is filled with hydrazine hydrate charging
Set 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, third paint mixing kettle 9 is connected to；First paint mixing kettle 7 obtains antiglossing pigment；Second paint mixing kettle 8 obtains anti-dazzle optical coating；Third
Paint mixing kettle 9 is spare.
Embodiment 1
(1) by isophorone diisocyanate, 2,2- dihydromethyl propionic acids/polytetrahydrofuran ether glycol (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：Residence time is 1.0 hours, and reaction temperature is controlled at 60 DEG C；Then it is pre- that it is passed through second again
Poly- kettle 2 carries out two sections of polymerizations：Residence time is 2.0 hours, and reaction temperature is controlled at 80 DEG C.
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer 3, triethylamine with triethylamine
It is 1.1 kgs/hour to be passed through speed, after being neutralized into salt 0.15 hour, is cooled to room temperature to get waterborne polyurethane prepolymer.
(3) waterborne polyurethane prepolymer is passed through the first high speed shear mixing emulsifier 4, is passed through ethylenediamine base ethanesulfonic acid sodium
The speed that is passed through of (mass concentration 0.6%) aqueous solution, ethylenediamine base ethanesulfonic acid sodium water solution is 64 kgs/hour, chain extending reaction
0.35 hour, stir speed (S.S.) was controlled in 1400rpm；It is then fed into the second high speed shear mixing emulsifier 5, hydrazine hydrate is with 1.8 public affairs
Jin/hour is continuously added dropwise, rear chain extending reaction 0.15 hour, and stir speed (S.S.) control is in 600rpm to get aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed with deionized water in the second static mixer 6, it is solid to adjust lotion
For content 30%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；It finally, will be deployed
Aqueous polyurethane emulsion is passed through the first paint mixing kettle 7 and metering adjuvant pigments slurry mixing (by percentage to the quality, antiglossing pigment packet
Include 80% aqueous polyurethane emulsion, 0.5% BYK-019 antifoaming agent, 3% BYK-333 levelling agents, 1% Borchi
Gel LW44 thickeners and 1.5% CoatOSil1770 curing agent, remaining as deionized water, each component summation is
100%) to get aqueous polyurethane antiglossing pigment, 60 ° of coating film, glossiness 2 shows excellent extinction effect.
Embodiment 2
(1) by benzene dimethylene diisocyanate, 2,2- dimethylolpropionic acids/polytetrahydrofuran ether glycol (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
It is passed through (or instillation) first prepolymerization kettle and carries out one-step polymerization：Residence time is 1.5 hours, and reaction temperature is controlled at 55 DEG C；Then
It is passed through the second prepolymerization kettle again and carries out two sections of polymerizations：Residence time is 2.0 hours, and reaction temperature is controlled at 85 DEG C.
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer with tripropyl amine (TPA), tripropyl amine (TPA) is logical
It is 1.6 kgs/hour to enter speed, after being neutralized into salt 0.25 hour, is cooled to room temperature to get waterborne polyurethane prepolymer.
(3) prepolymer is passed through the first high speed shear mixing emulsifier, ethylenediamine base ethanesulfonic 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.) is controlled in 1800rpm；It is then fed into
Two high speed shear mixing emulsifiers, hydrazine hydrate is with 1.8 kgs/hour of continuous dropwise additions, rear chain extending reaction 0.15 hour, stir speed (S.S.)
Control is in 800rpm to get aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed with deionized water in the second static mixer, it is solid to adjust lotion
For content 40%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；It finally, will be deployed
Aqueous polyurethane emulsion is passed through the first paint mixing kettle 7 and metering adjuvant pigments slurry mixing (by percentage to the quality, antiglossing pigment packet
Include 90% aqueous polyurethane emulsion, 3% BYK-141 antifoaming agent, 3% BYK-346 levelling agents, 0.5% Borchi
Gel LW44 thickeners and 0.5% CoatOSil1770 curing agent, remaining as deionized water, each component summation is
100%) to get aqueous polyurethane antiglossing pigment.
Embodiment 3
(1) by isophorone diisocyanate, 2,2- dihydromethyl propionic acids/polytetrahydrofuran ether glycol (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
Enter (or instillation) first prepolymerization kettle and carries out one-step polymerization：Residence time is 1.5 hours, and reaction temperature is controlled at 60 DEG C；Then again
It is passed through the second prepolymerization kettle and carries out two sections of polymerizations：Residence time is 2.5 hours, and reaction temperature is controlled at 80 DEG C.
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer with triethylamine, triethylamine is logical
It is 1.0 kgs/hour to enter speed, after being neutralized into salt 0.25 hour, is cooled to room temperature to get waterborne polyurethane prepolymer.
(3) prepolymer is passed through the first high speed shear mixing emulsifier, ethylenediamine base ethanesulfonic 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.) is controlled in 3000rpm；It is then fed into
Two high speed shear mixing emulsifiers, hydrazine hydrate is with 1.1 kgs/hour of continuous dropwise additions, rear chain extending reaction 0.15 hour, stir speed (S.S.)
Control is in 1000rpm to get aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed with deionized water in the second static mixer, it is solid to adjust lotion
For content 30%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；It finally, will be deployed
Aqueous polyurethane emulsion is passed through the second paint mixing kettle 8 and metering adjuvant pigments slurry mixing (by percentage to the quality, anti-dazzle optical coating
Including 70% aqueous polyurethane emulsion, 3% BYK-019 antifoaming agent, 3% BYK-333 levelling agents, 3% Borchi
Gel LW44 thickeners and 1.5% CoatOSil1770 curing agent, remaining as deionized water, each component summation is
100%) to get the anti-dazzle optical coating of aqueous polyurethane.
Embodiment 4
(1) by benzene dimethylene diisocyanate, 2,2- dihydromethyl propionic acids/polytetrahydrofuran ether glycol (mass ratio 1：
22) solution, isooctyl acid bismuth are continuously passed through (or drop with 15.3 kgs/hour, 33.4 kgs/hour, 6.5 Grams Per Hour speed respectively
Enter) the first prepolymerization kettle progress one-step polymerization：Residence time is 1.0 hours, and reaction temperature is controlled at 65 DEG C；Then it is passed through second again
Prepolymerization kettle carries out two sections of polymerizations：Residence time is 2.5 hours, and reaction temperature is controlled at 75 DEG C.
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer with triethylamine, triethylamine is logical
It is 1.0 kgs/hour to enter speed, after being neutralized into salt 0.15 hour, is cooled to room temperature to get 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.) is controlled in 2000rpm；It is then fed into
Second high speed shear mixing emulsifier, hydrazine hydrate is with 1.1 kgs/hour of continuous dropwise additions, rear chain extending reaction 0.25 hour, stirring speed
Rate control is in 800rpm to get aqueous polyurethane emulsion.
(4) aqueous polyurethane emulsion is continuously mixed with deionized water in the second static mixer, it is solid to adjust lotion
For content 20%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；It finally, will be deployed
Aqueous polyurethane emulsion is passed through the second paint mixing kettle 8 and metering adjuvant pigments slurry mixing (by percentage to the quality, anti-dazzle optical coating
Including 80% aqueous polyurethane emulsion, 0.5% BYK-141 antifoaming agent, 0.5% BYK-346 levelling agents, 3%
Borchi Gel LW44 thickeners and 0.1% CoatOSil1770 curing agent, remaining as deionized water, each component summation
For 100%) to get the anti-dazzle optical coating of aqueous polyurethane.
The test result of 1-4 of the embodiment of the present invention is shown in Table 1.
The quantitative measurement result of 1 aqueous polyurethane optical coating film of the embodiment of the present invention 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 and 60 ° of glossiness for applying example 2 are respectively that 2 and 3 are shown excellent close to zero diopter rank
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, good anti-glare properties energy is presented in embodiment 3 and embodiment 4.
Erdem of Dow Chemical Company etc. experiments have shown that, in isophorone diisocyanate-prepolymer system, isocyanic acid
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 carboxylic 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-1s of identical molal quantity, 3-propanediol (0.224mol/100g prepolymers),
It is respectively synthesized prepolymer under the same conditions, the former prepolymer viscosity is more much higher than the latter, almost differs 1 number at room temperature
Magnitude.It is a discovery of the invention that prepolymerization rate is too fast, hydrophilic chain extender segment in polyurethane molecular structure can be made to be unevenly distributed
It is even, as a result product property is caused to be deteriorated.And hydrophilic chain extender, polytetrahydrofuran ether glycol and di-isocyanate reaction are a pair of
Unexpectedly reaction is striven.At a lower temperature, hydroxyl activity is relatively low in hydrophilic chain extender, slower with reacting for diisocyanate, isocyanide
Acid esters general first and polytetrahydrofuran ether glycol (hydrophilic chain extender and the mass ratio of polytetrahydrofuran ether glycol 1：20~25)
Hydroxyl reaction.When system is in the condition of high temperature, the hydroxyl activity enhancing in hydrophilic chain extender adds with reacting for isocyanates
Soon.In addition, diisocyanate and hydroxyl react category exothermic reaction, in reaction process, system temperature easily soar to 80 DEG C with
On, at this point, the reactivity of hydrophilic chain extender increases, while temperature is difficult to control, it will make hydrophilic chain extender in polyurethane
It is unevenly distributed in strand, product property is caused to be deteriorated.Therefore the present invention controls prepolymerization technology using two benches heating, to reach
The purpose being evenly distributed in polyurethane molecular chain to acquisition hydrophilic chain extender.At this point, 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 insufficient in prepolymerisation stage.The present invention is continuous technique using pre-polymerization, neutralization and chain extension
Technical method realizes the preparation of aqueous polyurethane optical coating, and this method is continuously gathered with foreign countries major company existing aqueous polyurethanes
Conjunction technology is compared, and when avoiding addition hydrophilic chain extender dihydromethyl propionic acid, the strong hydrogen bonding formation of carboxylic acid group leads to pre-polymerization
The very high and uncontrollable problem of object viscosity, while preparation time can be shortened 1-2 hours, save energy consumption about 20-30%.
Claims (8)
1. the technique that a kind of continuity method prepares aqueous polyurethane optical coating, it is characterised in that include the following steps：
(1) by diisocyanate, hydrophilic chain extender/polytetrahydrofuran ether glycol solution, organo-metallic catalyst respectively with 15~
20 kgs/hour, 30~36 kgs/hour, 2~20 Grams Per Hour speed be continuously passed through or instill the first prepolymerization kettle carry out one section
Polymerization：Residence time 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 and carries out two
Duan Juhe：Residence time is 2.0~2.5 hours, and reaction temperature is controlled at 75~85 DEG C；Hydrophilic chain extender and polytetrahydrofuran ether
The mass ratio 1 of glycol：20~25；The hydrophilic chain extender is 2,2- dihydromethyl propionic acids and/or 2,2- dimethylolpropionic acids；
(2) two sections of polymer materials that step (1) obtains continuously are passed through the first static mixer, tertiary amines with tertiary amines neutralizer
It is 0.8~1.2 kg/hour that neutralizer, which is passed through speed, after being neutralized into salt 0.15~0.25 hour, is cooled to room temperature to get water
Property polyurethane prepolymer；
(3) waterborne polyurethane prepolymer is passed through the first high speed shear mixing emulsifier, is containing the water-soluble of sulfonate type chain extender
Chain extending reaction occurs while emulsification in liquid：The speed that is passed through of the sulfonate type chain extender aqueous solution of mass concentration 0.5~6% is
65~75 kgs/hour, chain extending reaction 0.25~0.35 hour, stir speed (S.S.) is controlled in 1400rpm~3200rpm；Then it send
Enter the second high speed shear mixing emulsifier, aqueous polyurethane emulsion is obtained by the reaction in the continuous hydrazine hydrate rear chain extender that is added dropwise：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 with deionized water in the second static mixer, to adjust emulsion solid content
20~45%, 0.5 times of aqueous polyurethane emulsion of deionized water speed of cooperation is passed through speed；It finally, will be deployed
Aqueous polyurethane emulsion is passed through paint mixing kettle and starches mixing with adjuvant pigments, 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 benzene dimethylene diisocyanate.
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 polytetrahydrofuran ether glycol molecular weight described in (1) is 1000g/mol.
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 organo-metallic catalyst described in (1) is one kind in isooctyl acid bismuth and dibutyl tin laurate.
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 tertiary amines neutralizer described in (2) is triethylamine and/or tripropyl amine (TPA).
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 sulfonate type chain extender described in (3) is ethylenediamine base ethanesulfonic acid sodium and/or ethylenediamine base propanesulfonate.
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 emulsion feed speed of (4) described second static mixer be prepare aqueous polyurethane emulsion all materials admission velocity it
With.
8. the technique that a kind of continuity method according to claim 1 prepares aqueous polyurethane optical coating, it is characterised in that：Institute
State BYK-019 and BYK-141 antifoaming agent, BYK-333 the and BYK-346 levellings that adjuvant pigments slurry includes Bi Ke chemical companies of Germany
Agent, the Borchi Gel LW44 thickeners of OMG companies of the U.S. and Momentive new high-tech materials company of the U.S.
CoatOSil1770 curing agent.
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| CN110818881B (en) * | 2019-11-22 | 2021-10-22 | 万华化学（北京）有限公司 | Preparation method of polyurethane ink resin, polyurethane ink resin prepared by preparation method and ink |
| CN112341590B (en) * | 2020-11-11 | 2021-09-10 | 中山大学 | Waterborne polyurethane and continuous preparation process thereof |
| CN113024757B (en) * | 2021-03-03 | 2021-12-14 | 四川大学 | Method for preparing waterborne polyurethane through prepolymerization-emulsification full-continuous method |
| 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 |
| CN114409553B (en) * | 2022-01-28 | 2023-02-14 | 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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| CN103073696B (en) * | 2013-01-30 | 2014-08-13 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
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