CN107759770A - A kind of preparation method of photo catalyzed polyurethane material - Google Patents
A kind of preparation method of photo catalyzed polyurethane material Download PDFInfo
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- CN107759770A CN107759770A CN201711121778.8A CN201711121778A CN107759770A CN 107759770 A CN107759770 A CN 107759770A CN 201711121778 A CN201711121778 A CN 201711121778A CN 107759770 A CN107759770 A CN 107759770A
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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
- C08G18/83—Chemically modified polymers
- C08G18/838—Chemically modified polymers by compounds containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention belongs to polyurethane material technical field, more particularly to a kind of preparation method of photo catalyzed polyurethane material, it is dissolved in by tetrabutyl titanate in the absolute ethyl alcohol containing polyvinylpyrrolidone, titanium dioxide parcel liquid is obtained after back flow reaction and ultrasonic reaction, then by adding polyurethane material N after being mixed with initiator, N dimethylacetamide solutions, obtain mixed liquor, heated microwave reaction and constant temperature processing, modified polyurethane solution is obtained, finally obtains modified polyurethane material by ultrasonic reaction and vacuum distillation reaction.The present invention has filled up blank of the polyurethane in photocatalytic self-cleaning functional area, realizes the compatible of polymer and nano titanium oxide, embodies good photocatalysis performance.
Description
Technical field
The invention belongs to polyurethane material technical field, and in particular to a kind of preparation method of photo catalyzed polyurethane material.
Background technology
Polyurethane material is deep to be favored by consumers in general due to its excellent physics and chemical property.In daily life
In, polyurethane products are widely applied to the fields such as clothes, case and bag, decoration, automobile, aviation and medical treatment.In the process used
In, polyurethane product is inevitably invaded and harassed by greasy filth, such as：Various dyestuffs, food beverage spot and it is various easily
Raw bacterium etc., and the washing of polyurethane is complicated with sterilization process and wastes the energy, and many puzzlements and trouble are brought to consumer.With
The worsening of environment, particularly recently the generation of global major pollution incident, consumer want to polyurethane product
More and more higher is sought, this also promotes scientific research personnel to carry out the research of related automatically cleaning technology.
Chinese patent CN1522795A, patent name are：A kind of photocatalytic self-cleaning film.A kind of photocatalysis is reported certainly
Cleaning film.The invention is prepared for double membrane structure, and superficial layer is filled by titanium dioxide；Bottom is to contain titanium dioxide, three oxygen
Change the composite membrane of two aluminium and tin ash.This membrane structure can be under natural light irradiation, effectively the characteristics of degraded harmful substance.
Chinese patent CN101525504A, patent name are：Photocatalytic self-cleaning film with self demixing buffer action
Agent and preparation method thereof.Titanium dioxide is added to by inorganic aqueous sol binding agent, resin emulsion or water dispersant by the invention,
It is prepared for the plastics with photocatalytic self-cleaning function.
Chinese patent CN101250596 and CN101250597, patent name are respectively：Contain nano-functional material
The preparation method and nano self-cleaning leather of self-cleaning leather or product or the preparation method of product.Two inventions are by nanoscale
Solid particle is mixed into Organic fluoride finishing agent；Then leather or product are sprayed using Organic fluoride finishing agent at room temperature
Apply, mopping or roller coat, make leather or product do not get wet, oily dirt free, there is self-cleaning function.
At present, photocatalytic self-cleaning function uses the inorganic nano-particles such as nano titanium oxide real as filler mostly
It is existing.Chinese patent CN101525504A, patent name are：Photocatalytic self-cleaning plastics with self demixing buffer action and its
Preparation method, the solid content of patent report nano titanium oxide could show the catalytic of light extraction when reaching more than 5%.Separately
Outside, nano titanium oxide is poor with polymer compatibility, and the nano titanium oxide being wrapped by can not play catalytic action, nanoscale
Titanium oxide inorganic particle easily comes off, and these problems result in the inorganic particulates such as nano titanium oxide can not be in polyurethane field
Realize photocatalytic self-cleaning function and industrialized production.
The content of the invention
For the problems of the prior art, the present invention provides a kind of preparation method of photo catalyzed polyurethane material, filled up
Polyurethane realizes the compatible of polymer and nano titanium oxide, embodied good in the blank of photocatalytic self-cleaning functional area
Good photocatalysis performance.
To realize above technical purpose, the technical scheme is that：A kind of preparation method of photo catalyzed polyurethane material,
Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 10-15min, until completely molten
Solution, form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 10-15min, then adds polyvinylpyrrolidone shape
Into scattered alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 1-3h in reactor, ultrasonic reaction 2-4h, titanium dioxide is obtained after cooling
Wrap up liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 3-5h in microwave reaction kettle, constant temperature processing 1-2h, obtains being modified poly- ammonia
Ester solution；
Step 6, by modified polyurethane solution ultrasonic reaction 30-50min, reaction 1-3h is then evaporated under reduced pressure, obtains being modified poly- ammonia
Ester material.
The mass concentration of the polyurethane material of solution A in the step 1 is 30-35%, the frequency of the sealing ultrasonic reaction
Rate is 1.5-3.5kHz, and ultrasonic temperature is 30-50 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.3-0.5MPa.
The concentration of tetrabutyl titanate in the step 2 is 5-10g/L, and the concentration of the polyvinylpyrrolidone is 15-
20g/L, the churned mechanically mixing speed are 3000-3500r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 70-80 DEG C, and condensed water goes out
Mouth temperature is 40-50 DEG C.
Ultrasonic reaction frequency in the step 3 is 5.5-9.5kHz, and ultrasonic reaction is reacted using water bath sonicator, and temperature is
50-70 DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 20-40% of tetrabutyl titanate mole, and the initiator used
Ammonium sulfate, the process for dispersing are mechanical mixing method, and mixing speed 1500-3500r/min, the rate of addition is 10-
15mL/min, the mixing speed are 3500-5500r/min.
The temperature of heating microwave reaction in the step 5 is 120-150 DEG C, microwave power 100-200W, the perseverance
The temperature of temperature processing is 90-100 DEG C.
As an improvement, the microwave heating response uses gradient reaction system, its reactions steps is as follows：
| Temperature | Power | Time |
| 50-80℃ | 100-120W | 10-30min |
| 100-110℃ | 150-170W | 20-30min |
| 140-150℃ | 180-200W | Remaining time |
The frequency of ultrasonic reaction in the step 6 is 8.5-12.5kHz, and temperature is 70-80 DEG C, the pressure of the vacuum distillation
For the 40-60% of atmospheric pressure, temperature is 70-80 DEG C.
Polyurethane material is dissolved in DMA by step 1, by it by way of sealing ultrasonic reaction
Quick dissolving, form the lysate of polyurethane.
Tetrabutyl titanate is put into absolute ethyl alcohol by step 2, is formed dissolving by stirring, is then added polyvinylpyrrolidine
Tetrabutyl titanate is uniformly distributed in alcohol liquid by ketone as dispersant.
Scattered alcohol liquid back flow reaction is ensured contact of the polyvinylpyrrolidone with tetrabutyl titanate by step 3, is ensured simultaneously
The dispersive property of tetrabutyl titanate, ultrasonic reaction can open the connecting key of tetrabutyl titanate, form TiO 2 particles, and
And parcel is formed in the presence of polyvinylpyrrolidone, obtain the alcohol liquid of polyvinylpyrrolidone parcel titanium dioxide.
Initiator added in parcel liquid in step 4 can be formed it is well mixed, and in the work of polyvinylpyrrolidone
Good dispersion is formed with lower, ensures that initiator is scattered in liquid is wrapped up；Parcel drop is added to the dissolving of polyurethane
In liquid, the dissolubility of DMA and absolute ethyl alcohol is not only make use of, while also utilizes polyvinylpyrrolidone
Nano oxidized titanium particle and initiator are evenly distributed in polyurethane.
Step 5 can provide energy by heating microwave reaction, also provide microwave treatment kinetic energy, improve the initiation of initiator
Effect, nano-titania particle is acted on to polyurethane, and the link for forming polyurethane is modified, by way of constant temperature processing
Molecular activity is reduced, ensures that the photocatalysis performance of polyurethane is modified.
Modified polyurethane solution ultrasonic reaction is reached scattered effect by step 6, by solvent by way of vacuum distillation
Remove, obtain the polyurethane material of photocatalysis performance modification.
The present invention is dissolved in the absolute ethyl alcohol containing polyvinylpyrrolidone by tetrabutyl titanate, back flow reaction and ultrasound
Titanium dioxide parcel liquid is obtained after reaction, then by adding polyurethane material-N, N- dimethylacetamide after being mixed with initiator
Amine aqueous solution, mixed liquor is obtained, heated microwave reaction and constant temperature processing, obtains modified polyurethane solution, it is finally anti-by ultrasound
Modified polyurethane material should be obtained with reaction is evaporated under reduced pressure.
From the above, it can be seen that the present invention possesses advantages below：
1. the present invention has filled up blank of the polyurethane in photocatalytic self-cleaning functional area, polymer and nanometer titanium dioxide are realized
Titanium it is compatible, embody good photocatalysis performance.
2. polyurethane material is readily dissolved in the organic solvent of DMA by the present invention, and with good
Good mouldability and plasticity, while also provide liquid-phase reaction condition for modification.
3. photo catalyzed polyurethane material prepared by the present invention can produce substantial amounts of Active Radicals Produced, make photocatalytic self-cleaning
Polyurethane material can efficiently remove depollution.
4. the present invention can promote initiator for reaction using microwave handling method, nano titanium oxide is connected to polyurethane
On, substantially increase the firmness of inorganic particulate.
Embodiment
Describe the present invention in detail in conjunction with the embodiments, but any restriction is not done to the claim of the present invention.
Embodiment 1
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 10min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 10min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 1h in reactor, ultrasonic reaction 2h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 3h in microwave reaction kettle, constant temperature processing 1h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 30min, reaction 1h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 30%, the frequency of the sealing ultrasonic reaction
For 1.5kHz, ultrasonic temperature is 30 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.3MPa.
The concentration of tetrabutyl titanate in the step 2 is 5g/L, and the concentration of the polyvinylpyrrolidone is 15g/L,
The churned mechanically mixing speed is 3000r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 70 DEG C, condensation-water drain temperature
Spend for 40 DEG C.
Ultrasonic reaction frequency in the step 3 is 5.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 50
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 20% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 1500r/min, the rate of addition is 10mL/min, described to stir
It is 3500r/min to mix speed.
The temperature of heating microwave reaction in the step 5 is 120 DEG C, microwave power 100W, the constant temperature processing
Temperature is 90 DEG C.
The frequency of ultrasonic reaction in the step 6 is 8.5kHz, and temperature is 70 DEG C, and the pressure of the vacuum distillation is big
The 40% of air pressure, temperature are 70 DEG C.
Embodiment 2
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 15min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 15min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 3h in reactor, ultrasonic reaction 4h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 5h in microwave reaction kettle, constant temperature processing 2h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 50min, reaction 3h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 35%, the frequency of the sealing ultrasonic reaction
For 3.5kHz, ultrasonic temperature is 50 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.5MPa.
The concentration of tetrabutyl titanate in the step 2 is 10g/L, and the concentration of the polyvinylpyrrolidone is 20g/L,
The churned mechanically mixing speed is 3500r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 80 DEG C, condensation-water drain temperature
Spend for 50 DEG C.
Ultrasonic reaction frequency in the step 3 is 9.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 70
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 40% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 3500r/min, the rate of addition is 15mL/min, described to stir
It is 5500r/min to mix speed.
The temperature of heating microwave reaction in the step 5 is 150 DEG C, microwave power 200W, the constant temperature processing
Temperature is 100 DEG C.
The frequency of ultrasonic reaction in the step 6 is 12.5kHz, and temperature is 80 DEG C, and the pressure of the vacuum distillation is
The 60% of atmospheric pressure, temperature are 80 DEG C.
Embodiment 3
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 12min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 12min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 2h in reactor, ultrasonic reaction 3h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 4h in microwave reaction kettle, constant temperature processing 2h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 40min, reaction 2h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 32%, the frequency of the sealing ultrasonic reaction
For 2.5kHz, ultrasonic temperature is 40 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.4MPa.
The concentration of tetrabutyl titanate in the step 2 is 8g/L, and the concentration of the polyvinylpyrrolidone is 18g/L,
The churned mechanically mixing speed is 3200r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 75 DEG C, condensation-water drain temperature
Spend for 45 DEG C.
Ultrasonic reaction frequency in the step 3 is 7.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 60
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 30% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 1500r/min, the rate of addition is 13mL/min, described to stir
It is 4500r/min to mix speed.
The temperature of heating microwave reaction in the step 5 is 140 DEG C, microwave power 150W, the constant temperature processing
Temperature is 95 DEG C.
The frequency of ultrasonic reaction in the step 6 is 8.5-12.5kHz, and temperature is 70-80 DEG C, the vacuum distillation
Pressure is the 40-60% of atmospheric pressure, and temperature is 70-80 DEG C.
Embodiment 4
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 12min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 12min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 2h in reactor, ultrasonic reaction 3h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 4h in microwave reaction kettle, constant temperature processing 2h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 40min, reaction 2h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 32%, the frequency of the sealing ultrasonic reaction
For 2.5kHz, ultrasonic temperature is 40 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.4MPa.
The concentration of tetrabutyl titanate in the step 2 is 8g/L, and the concentration of the polyvinylpyrrolidone is 18g/L,
The churned mechanically mixing speed is 3200r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 75 DEG C, condensation-water drain temperature
Spend for 45 DEG C.
Ultrasonic reaction frequency in the step 3 is 7.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 60
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 30% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 1500r/min, the rate of addition is 13mL/min, described to stir
It is 4500r/min to mix speed.
The temperature of constant temperature processing in the step 5 is 95 DEG C；The microwave heating response uses gradient reactant
System, its reactions steps are as follows：
| Temperature | Power | Time |
| 50℃ | 100W | 10min |
| 100℃ | 150W | 20min |
| 140℃ | 180W | Remaining time |
The frequency of ultrasonic reaction in the step 6 is 10.5kHz, and temperature is 75 DEG C, and the pressure of the vacuum distillation is air
The 50% of pressure, temperature are 75 DEG C.
Embodiment 5
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 12min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 12min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 2h in reactor, ultrasonic reaction 3h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 4h in microwave reaction kettle, constant temperature processing 2h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 40min, reaction 2h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 32%, the frequency of the sealing ultrasonic reaction
For 2.5kHz, ultrasonic temperature is 40 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.4MPa.
The concentration of tetrabutyl titanate in the step 2 is 8g/L, and the concentration of the polyvinylpyrrolidone is 18g/L,
The churned mechanically mixing speed is 3200r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 75 DEG C, condensation-water drain temperature
Spend for 45 DEG C.
Ultrasonic reaction frequency in the step 3 is 7.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 60
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 30% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 1500r/min, the rate of addition is 13mL/min, described to stir
It is 4500r/min to mix speed.
The temperature of constant temperature processing in the step 5 is 95 DEG C；The microwave heating response uses gradient reactant
System, its reactions steps are as follows：
| Temperature | Power | Time |
| 80℃ | 120W | 30min |
| 110℃ | 170W | 30min |
| 150℃ | 200W | Remaining time |
The frequency of ultrasonic reaction in the step 6 is 9.5kHz, and temperature is 75 DEG C, and the pressure of the vacuum distillation is atmospheric pressure
45%, temperature be 75 DEG C.
Embodiment 6
A kind of preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：
Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 12min, until be completely dissolved,
Form solution A；
Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 12min, then adds polyvinylpyrrolidone and formed and divided
Dissipate alcohol liquid；
Step 3, scattered alcohol liquid is put into back flow reaction 2h in reactor, ultrasonic reaction 3h, titanium dioxide parcel is obtained after cooling
Liquid；
Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain
To mixed liquor；
Step 5, mixed liquor is put into heating microwave reaction 4h in microwave reaction kettle, constant temperature processing 2h, it is molten obtains modified polyurethane
Liquid；
Step 6, by modified polyurethane solution ultrasonic reaction 40min, reaction 2h is then evaporated under reduced pressure, obtains modified polyurethane material
Material.
The mass concentration of the polyurethane material of solution A in the step 1 is 32%, the frequency of the sealing ultrasonic reaction
For 2.5kHz, ultrasonic temperature is 40 DEG C.
The pressure of sealing ultrasonic reaction in the step 1 is 0.4MPa.
The concentration of tetrabutyl titanate in the step 2 is 8g/L, and the concentration of the polyvinylpyrrolidone is 18g/L,
The churned mechanically mixing speed is 3200r/min.
Back flow reaction in the step 3 is using condensation water cooling, and the temperature of back flow reaction is 75 DEG C, condensation-water drain temperature
Spend for 45 DEG C.
Ultrasonic reaction frequency in the step 3 is 7.5kHz, and ultrasonic reaction is reacted using water bath sonicator, temperature 60
DEG C, the cooling uses nitrogen cooling method.
Initiator addition in the step 4 is the 30% of tetrabutyl titanate mole, and the initiator uses persulfuric acid
Ammonium, the process for dispersing are mechanical mixing method, and mixing speed 1500r/min, the rate of addition is 13mL/min, described to stir
It is 4500r/min to mix speed.
The temperature of constant temperature processing in the step 5 is 95 DEG C；The microwave heating response uses gradient reactant
System, its reactions steps are as follows：
| Temperature | Power | Time |
| 50℃ | 110W | 20min |
| 100℃ | 160W | 25min |
| 150℃ | 200W | Remaining time |
The frequency of ultrasonic reaction in the step 6 is 11.5kHz, and temperature is 75 DEG C, and the pressure of the vacuum distillation is air
The 55% of pressure, temperature are 75 DEG C.
In summary, the present invention has advantages below：
1. the present invention has filled up blank of the polyurethane in photocatalytic self-cleaning functional area, polymer and nanometer titanium dioxide are realized
Titanium it is compatible, embody good photocatalysis performance.
2. polyurethane material is readily dissolved in the organic solvent of DMA by the present invention, and with good
Good mouldability and plasticity, while also provide liquid-phase reaction condition for modification.
3. photo catalyzed polyurethane material prepared by the present invention can produce substantial amounts of Active Radicals Produced, make photocatalytic self-cleaning
Polyurethane material can efficiently remove depollution.
4. the present invention can promote initiator for reaction using microwave handling method, nano titanium oxide is connected to polyurethane
On, substantially increase the firmness of inorganic particulate.
It is understood that above with respect to the specific descriptions of the present invention, it is merely to illustrate the present invention and is not limited to this
Technical scheme described by inventive embodiments.It will be understood by those within the art that still the present invention can be carried out
Modification or equivalent substitution, to reach identical technique effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (10)
- A kind of 1. preparation method of photo catalyzed polyurethane material, it is characterised in that：Its step is as follows：Step 1, polyurethane material is placed in DMA, seals ultrasonic reaction 10-15min, until completely molten Solution, form solution A；Step 2, tetrabutyl titanate is added into absolute ethyl alcohol, mechanical agitation 10-15min, then adds polyvinylpyrrolidone shape Into scattered alcohol liquid；Step 3, scattered alcohol liquid is put into back flow reaction 1-3h in reactor, ultrasonic reaction 2-4h, titanium dioxide is obtained after cooling Wrap up liquid；Step 4, initiator is added in titanium dioxide wraps up liquid, is added dropwise in solution A, stirs after being uniformly dispersed, obtain To mixed liquor；Step 5, mixed liquor is put into heating microwave reaction 3-5h in microwave reaction kettle, constant temperature processing 1-2h, obtains being modified poly- ammonia Ester solution；Step 6, by modified polyurethane solution ultrasonic reaction 30-50min, reaction 1-3h is then evaporated under reduced pressure, obtains being modified poly- ammonia Ester material.
- A kind of 2. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 1 In the mass concentration of polyurethane material of solution A be 30-35%, the frequency of the sealing ultrasonic reaction is 1.5-3.5kHz, Ultrasonic temperature is 30-50 DEG C.
- A kind of 3. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 1 In the pressure of sealing ultrasonic reaction be 0.3-0.5MPa.
- A kind of 4. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 2 In the concentration of tetrabutyl titanate be 5-10g/L, the concentration of the polyvinylpyrrolidone is 15-20g/L, the mechanical agitation Mixing speed be 3000-3500r/min.
- A kind of 5. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 3 In back flow reaction using condensation water cooling, the temperature of back flow reaction is 70-80 DEG C, and condensation-water drain temperature is 40-50 DEG C.
- A kind of 6. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 3 In ultrasonic reaction frequency be 5.5-9.5kHz, ultrasonic reaction is reacted using water bath sonicator, and temperature is 50-70 DEG C, the cooling Using nitrogen cooling method.
- A kind of 7. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 4 In initiator addition be tetrabutyl titanate mole 20-40%, the initiator uses ammonium persulfate, the scattered side Method is mechanical mixing method, and mixing speed 1500-3500r/min, the rate of addition is 10-15mL/min, the stirring speed Spend for 3500-5500r/min.
- A kind of 8. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 5 In the temperature of heating microwave reaction be 120-150 DEG C, microwave power 100-200W, the temperature of the constant temperature processing is 90- 100℃。
- A kind of 9. preparation method of photo catalyzed polyurethane material according to claim 8, it is characterised in that：The microwave adds Thermal response uses gradient reaction system, and its reactions steps is as follows：
Temperature Power Time 50-80℃ 100-120W 10-30min 100-110℃ 150-170W 20-30min 140-150℃ 180-200W Remaining time - A kind of 10. preparation method of photo catalyzed polyurethane material according to claim 1, it is characterised in that：The step 6 In the frequency of ultrasonic reaction be 8.5-12.5kHz, temperature is 70-80 DEG C, and the pressure of the vacuum distillation is the 40- of atmospheric pressure 60%, temperature is 70-80 DEG C.
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Application publication date: 20180306 |