Functionalised polyethers initiator and its synthesis and the application in polyethers synthesis
Technical field
The present invention relates to a kind of functionalised polyethers initiator and its synthetic methods and the application in polyethers synthesis, and belonging to has
Machine field of functional materials.
Background technique
With the development of artificial intelligence, demand of the people to functional intellectual material is increasingly improved.It is keeping passing
In the case where commons material inherent advantages, its new functionality and correspondence are assigned, this will expand the material in novel field
Using.
Traditional polyethers is initiator generally by fatty alcohol or aromatic alcohol, polymerize different number ethylene oxide or
Propylene oxide and obtain, be widely used in fields such as polyurethane synthesis, nonionic surfactants.However as the development of technology,
Demand of the downstream client to functional special polyether increasingly improves, this, which just needs to develop, has functional initiator for gathering
The synthesis of ether, to assign product new functionality.
Azobenzene is a kind of organic functional compound with photoisomerization performance, under ultraviolet light, azo
Benzene molecular can be changed into metastable cis-structure from stable transconfiguration, under dark, visible light or heating condition,
Again transconfiguration can be returned to from cis-structure.The change of azobenzene configuration will lead to molecular length, energy etc. and change,
So as to be embodied in the variation of the ultra-violet absorption spectrum of molecule.CN 107213843A report a kind of azo benzene-type it is non-from
The preparation method of sub- surfactant, by the photoisomerization of azobenzene molecule, the steric hindrance using cis-trans configuration is poor
Different change its bubble film surface alignment tightness degree, realize low concentration, high foam stabilizing effect.
This patent has synthesized a kind of azobenzene polyalcohol of racemosus by MOLECULE DESIGN, and it is used for polyethers synthesis.Phase
Than in common polyether initiator, which has optical Response, while compared to the single azobenzene molecule reported before, more
The photoresponse degree of branch structural molecule is higher, and speed is faster.Polyether polyol based on the preparation of this molecule is in washing, demulsifier etc.
Field is with a wide range of applications, and the presence of optical Response molecule can be conducive to detect polyether polyol in the solution residual
Allowance can also be advantageously implemented long-distance intelligent manipulation by the performance of lighting change polyether product.
Summary of the invention
In order to expand polyether product in the application in intelligent response field, this patent has synthesized a kind of novel functional form polyethers
Initiator, and it is synthesized applied to polyethers.
According to the first aspect of the invention, a kind of functionalised polyethers initiator is provided, it is poly- for novel racemosus azobenzene
Ether, structural formula are as follows:
Wherein, R is each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy, C1-C4 acidic group, be preferably selected from F,
Cl, Br, methyl, methoxyl group, carboxyl etc., n are the integer of 1-4.
Invention further provides a kind of functionalised polyethers, structural formula is as follows:
Wherein, R is each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-4 alkoxy, C1-C4 acidic group, be preferably selected from F,
Cl, Br, methyl, methoxyl group, carboxyl etc., n are the integer of 1-4.
At least one of a=0-200, b=0-200, a or b are not 0,
According to the third aspect of the present invention, the preparation method of above-mentioned functionalised polyethers initiator is provided, this method comprises:
(A) aniline of metering or substituted aniline are added in reaction kettle, addition acid regulation system pH is 1-6, and nitrogen is set
After changing, under 60-100 DEG C of reaction temperature, glyoxal is added in reaction kettle and is reacted, be neutralized to neutrality, remove system
In solvent and unreacted aniline or substituted aniline, the solution cooling after removing solvent obtains four aniline or substituted anilinic second
Crude product is for example carried out column chromatography for separation purification by alkane crude product, obtains four aniline or substituent group anilino- ethane;
(B) make 4- aminobenzene methanol or 4- amino R substituent benzyl alcohol and ammonium persulfate-sodium bisulfate (Oxone) in nitrogen
Protection lower reaction will wash after reaction after precipitating filtering, dry to obtain to nitrosobenzene methanol or to nitroso R substituent benzene first
Alcohol;
(C) replace by four anilino- ethane or four substituent group anilino- ethane and to nitrosobenzene methanol or to nitroso R
Base benzyl alcohol reacts under nitrogen protection, after reaction, water (such as distilled water) is added into system, precipitating is precipitated, after filtering
It collects filter cake and washs, vacuum drying obtains four (4- methylol azobenzene) ethane crude products of different substituents, by crude product
Such as column chromatography for separation purification is carried out, obtain four (4- methylol azobenzene) ethane compounds of different substituents.
According to the fourth aspect of the present invention, provide the preparation method of functionalised polyethers, above-mentioned steps (A)-(C) it
Further include: afterwards
(D) in the presence of a catalyst, make four (the 4- methylol azobenzene) ethane compounds and ring of different substituents
Oxidative ethane and/or propylene oxide reaction.
The reaction of step (A) can in the presence of a solvent, the preferred methanol of solvent, ethyl alcohol, the tert-butyl alcohol, toluene equal solvent
One of or it is a variety of, preferably methanol, the amount of solvent can be 0.2-2 times of aniline dosage, preferably 0.33-0.5 times.
The above-mentioned preparation method the step of in (A), the molar ratio of aniline or substituted aniline and glyoxal can be 1:0.1-
0.25, preferably 0.15~0.2.
In step (B), mole of 4- aminobenzene methanol or 4- amino R substituent benzyl alcohol and ammonium persulfate-sodium bisulfate
Than that can be 1:2~4, preferably 2.2~2.5.
In step (C), four anilino- ethane or four substituent group anilino- ethane and to nitrosobenzene methanol or to nitrous
The molar ratio of base R substituent benzyl alcohol can be 1:2~10, preferably 1:4-4.5.
In step (D), four (the 4- methylol azobenzene) ethane compounds and ethylene oxide and/or ring of different substituents
The mass ratio of Ethylene Oxide can be 1:1~20, preferably 1:8-12.The ratio of ethylene oxide and propylene oxide can be arbitrary.
In a specific embodiment, the preparation of above-mentioned functionalised polyethers initiator and functionalised polyethers includes following step
It is rapid:
1) synthesis of four anilino- ethane: by the aniline of metering, solvent, (mass ratio of aniline and solvent is 1:0.2-1, excellent
1:0.33-0.5 is selected, methanol, ethyl alcohol, propyl alcohol, the tert-butyl alcohol, toluene etc., preferably methanol can be used in solvent) it is added to reaction kettle
In, addition acid regulation system pH is 1-6, and nitrogen is replaced three times, and reaction temperature is 60-100 DEG C, is added glyoxal using constant-flux pump
Enter in reaction kettle, coutroi velocity 1-5mL/min, charging finishes that the reaction was continued 4-10 hours, in sodium bicarbonate or sodium carbonate
With extremely neutral, solvent and unreacted under conditions of system temperature is 100-120 DEG C, vacuum degree -0.1Mpa in removing system
Aniline, remove solvent after solution cooling obtains four anilino- ethane crude products.Crude product is subjected to column chromatography for separation purification
(silica gel is stationary phase, CH2Cl2/ ethyl acetate is eluent), obtain product.
2) synthesis to nitrosobenzene methanol: the 4- aminobenzene methanol for weighing 1 equivalent, which is dissolved in, fills 100-1000mL bis-
In the round-bottomed flask of chloromethanes.The ammonium persulfate-sodium bisulfate (Oxone) of 2-2.5 equivalent is dissolved in 1000-3000mL distillation
In water.Under nitrogen protection, Oxone solution is added drop-wise in round-bottomed flask, reacts at room temperature 2-6h, there is Precipitation.It will precipitating
It is washed repeatedly after filtering with water, it is dry to obtain crude product.
3) synthesis of four (4- methylol azobenzene) ethane: pair of four anilino- ethane and 4-4.5 equivalent of 1 equivalent is weighed
Nitrosobenzene methanol is dissolved in the glacial acetic acid (AcOH) and DMSO in the mixed solvent that volume ratio is 1:1.Under nitrogen protection, 25-60
DEG C reaction 24-90h.After reaction, distilled water is added into system, there are a large amount of Precipitations.Filter cake and anti-is collected after filtering
After backwashing is washed, and vacuum drying obtains crude product.Crude product is carried out column chromatography for separation purification, and (silica gel is stationary phase, CH2Cl2/MeOH
For eluent), obtain product.
4) synthetic route of four (4- methylol azobenzene) ethane polyethers is known conventional polyether synthesis technology.This field
Technical staff it is according to the present invention introduction combine the prior art can rationally determine initiator, catalyst type, catalyst amount,
Initiator/EO/PO moles of material ratio, reaction temperature, reaction pressure.Applicable catalyst include NaOH, KOH, Na, NaH,
CHO3Na、CHO3K, bimetallic catalyst, alkaline-earth metal catalyst, phosphazene catalyst, lewis acid catalyst etc., preferably alkali gold
Metal catalyst.Initiator, ethylene oxide and the total restatement of propylene oxide that dosage about catalyst is reacted according to investment, generally
0.02wt%~1.0wt% is selected, is preferably 0.05~0.5wt%.Initiator/EO/PO molar ratio be 1/0~300/0~
300, preferably 1/20~100/40~150.Reaction temperature is 80-160 DEG C, preferably 100-130 DEG C.Reaction pressure range be-
0.1MPa-0.6MPa, preferably control pressure are not higher than 0.4MPa.About the block sequence mode of block polyether, by changing EO
And/or PO is passed through the sequence of reaction and is designed.It, can be by the way that different quality ratio be added simultaneously about the synthesis of random copolymerization ether
EO and PO to obtaining copolyether.
By taking aniline as an example, the synthetic route of four anilino- ethane is as follows:
It is as follows to the synthetic route of nitrosobenzene methanol:
Four (4- methylol azobenzene) ethane, the synthetic route of four (4- methylol azobenzene) ethane polyethers are as follows:
At least one of a=0-200, b=0-200, a and b are not 0,
Change aniline into substituted aniline, such as ortho position, meta-substituent (such as F, Cl, Br, methyl, methoxyl group, carboxyl)
The functionalised polyethers initiator and functionalised polyethers for having other substituent groups can be made on phenyl ring in substituted aniline.
Invention further provides above-mentioned functionalised polyethers for colouring art or the purposes in crude oil demulsification field.
The specific method that the present invention prepares a kind of functionalised polyethers initiator includes following several key components: described four
The raw material that the synthesis of anilino- ethane uses for aniline, it is other containing ortho position, meta-substituent (such as F, Cl, Br, methyl, methoxyl group,
Carboxyl etc.) aromatic series aniline identical route can also be used synthesize corresponding product.The synthesis of the four anilino- ethane
It is 1-6 catalysis reaction by control system pH, it is general to select the acid for not containing double bond, such as hydrochloric acid.It is described to nitrosobenzene first
The synthesis of alcohol uses Oxone as oxidant, reacts more mild, and reaction process is easy to control, compared to strong oxidizer,
The peroxidating by-product that Oxone reaction generates is less.This method is not limited only to using 4- aminobenzene methanol be raw material, other containing neighbour
Position, the p-aminophenyl methanol of meta-substituent (such as F, Cl, Br, methyl, methoxyl group, carboxyl), equal amido phenenyl alcohol etc. are contained
The anil of hydroxyl can also be used this method and synthesize corresponding product.The synthesis of four (4- methylol azobenzene) ethane uses
The mixed solvent of glacial acetic acid and DMSO, DMSO is not involved in reaction, but can increase the solubility of reactant, so that two kinds of reactants
It is uniformly mixed, is more advantageous to quickening reaction speed.The synthesis of polyethers mainly controls reaction temperature and catalyst choice and dosage, root
According to the difference that properties of product require, the polyethers with different EO/PO ratios and copolymeric structure is synthesized.
Compared with prior art the present invention has the advantage that
1. the functionalised polyethers initiator of invention synthesis is a kind of new structural molecule, have not been reported at present.Synthesis
Molecule be the azobenzene molecule with racemosus structure, compare single azobenzene molecule, the molecular isomerism degree is higher, to light
It is more sensitive.
2. the synthetic route of invention design, reaction condition is more mild, and yield is higher, especially to nitrosobenzene first
The synthesis of pure and mild four (4- methylol azobenzene) ethane can be completed under conditions of close to room temperature, react safer.
3. belonging to functional product based on the polyether product that the novel initiator synthesizes, can be produced by Illumination adjusting polyethers
The performance of product, this is beneficial to realize performance remote control and regulation.Meanwhile solubility, residual quantity etc. of the polyether product in dicyandiamide solution
Index can also be tested by UV absorption and is quickly obtained, this is beneficial to it in fields such as crude oil demulsifier, drug dispersing agents
It is applied.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
It utilizes1H NMR (Varian INOVA 500MHz) is further to four (4- methylol azobenzene) ethanes of preparation
Compound carries out chemical structure test.Method for making sample is as follows: azobenzene powder dry on a small quantity being added in nuclear magnetic tube, deuterium is added
It is dissolved for dimethyl sulfoxide (DMSO-d6), carries out test characterization after ultrasonic disperse is uniform.Test scope: 0~16ppm.
Utilize four (4- methylol azobenzene) ethanes of high resolution mass spectrum (Waters Xevo G2QTof) test preparation
The molecular weight of compound.Sample powder after taking a small amount of drying is dissolved in methanol or acetonitrile and tests.
Embodiment 1
1) synthesis of four anilino- ethane: the aniline of 1kg, 0.5kg methanol are added in 3L reaction kettle, and hydrochloric acid tune is added
Section system pH is 1, and nitrogen is replaced three times, and reaction temperature is 60 DEG C, glyoxal is added in reaction kettle using constant-flux pump, control stream
Speed is 1mL/min, and glyoxal 93g is added altogether.Charging finishes that the reaction was continued 4 hours, neutrality is neutralized to sodium bicarbonate, in system
Temperature is 100 DEG C, solvent and unreacted aniline under conditions of vacuum degree -0.1Mpa in removing system, after removing solvent
Solution cooling obtains four anilino- ethane crude products.Crude product is carried out column chromatography for separation purification, and (silica gel is stationary phase, CH2Cl2/
Ethyl acetate is eluent), obtain product.
2) it the synthesis to nitrosobenzene methanol: weighs 1000g 4- aminobenzene methanol and is dissolved in and fill 100mL methylene chloride
Round-bottomed flask in.The Oxone of 2 equivalents is dissolved in 3000mL distilled water.Under nitrogen protection, Oxone solution is added dropwise
Into round-bottomed flask, 2h is reacted at room temperature, there is Precipitation.It will be washed repeatedly after precipitating filtering with water, it is dry to obtain crude product.
3) synthesis of four (4- methylol azobenzene) ethane: weigh 600g four anilino- ethane and 4 equivalents to nitrous
Base benzyl alcohol is dissolved in the glacial acetic acid (AcOH) and DMSO in the mixed solvent that volume ratio is 1:1.Under nitrogen protection, 25 DEG C of reactions
24h.After reaction, distilled water is added into system, there are a large amount of Precipitations.Filter cake is collected after filtering and is washed repeatedly, very
Sky is dry to obtain crude product.Crude product is carried out column chromatography for separation purification, and (silica gel is stationary phase, CH2Cl2/ MeOH is eluent),
Obtain four (4- methylol azobenzene) ethane products (1H NMR (500MHz, DMSO-d6): δ=8.06 (d, 8H;Ar-H),
7.74ppm(d,8H;Ar-H),7.69ppm(d,4H;Ar-H),7.67ppm(d,4H;Ar-H),6.78ppm(d,8H;Ar-H),
5.72ppm(s,Br,4H,OH),4.15ppm(s,8H;Ar-CH2),3.75ppm(s,2H;CH).HRMS-ESI:m/z:
870.3599(calcd.for[M+H]+,870.3605)。)。
4) synthesis of four (4- methylol azobenzene) ethane polyethers: to stirring, heating mantle and internal water cooling coil pipe
Four (4- methylol azobenzene) ethane 856g, 2.0g NaOH (0.05wt%) are put into 10L reaction kettle, seal reaction kettle.Nitrogen
Displacement three times, opens stirring, is warming up to 100 DEG C and is dehydrated at -0.1MPa, then keeps 100 DEG C, is gently passed through epoxy
Ethane, the logical material speed by controlling ethylene oxide keep reaction pressure < 0.3MPa, after being passed through ethylene oxide total 3520g
Stop charging, 100 DEG C progress aging reaction 3 hours;90 DEG C are cooled the temperature to, is neutralized with acetic acid, and is carried out at -0.1MPa
It is de- single, be cooled to room temperature four (4- methylol azobenzene) ethane polyoxyethylene ether (hydroxyl value: 56.2mg KOH/g, PDI:1.08,
Viscosity: 25 DEG C of 1502cP@).
Embodiment 2
1) the 3- fluoroaniline of 1.5kg, 0.5kg methanol the synthesis of four (3- fluoroanilino) ethane: are added to 3L reaction kettle
In, it is 3.5 that hydrochloric acid regulation system pH, which is added, and nitrogen is replaced three times, and reaction temperature is 80 DEG C, and glyoxal is added using constant-flux pump
In reaction kettle, glyoxal 136g is added in coutroi velocity 3mL/min altogether.Charging finishes that the reaction was continued 7 hours, uses sodium bicarbonate
It is neutralized to neutrality, solvent under conditions of system temperature is 110 DEG C, vacuum degree -0.1Mpa in removing system, after removing solvent
Solution cooling obtain four (3- fluoroanilino) ethane crude products.Crude product is carried out column chromatography for separation purification, and (silica gel is to fix
Phase, CH2Cl2/ ethyl acetate is eluent), obtain product.
2) it the synthesis of the fluoro- 4- nitrosobenzene methanol of 2-: weighs the fluoro- 4- aminobenzene methanol of 1500g 2- and is dissolved in and fill
In the round-bottomed flask of 550mL methylene chloride.The Oxone of 2.25 equivalents is dissolved in 2000mL distilled water.Under nitrogen protection,
Oxone solution is added drop-wise in round-bottomed flask, 4h is reacted at room temperature, there is Precipitation.It will be washed repeatedly, done with water after precipitating filtering
Dry acquisition crude product.
3) four (3- fluoroanilino) ethane of 800g the synthesis of four (2,2 '-two fluoro- 4- methylol azobenzene) ethane: are weighed
The glacial acetic acid (AcOH) and DMSO in the mixed solvent that volume ratio is 1:1 are dissolved in the fluoro- 4- nitrosobenzene methanol of 2- of 4.25 equivalents.
Under nitrogen protection, 40 DEG C of reaction 60h.After reaction, distilled water is added into system, there are a large amount of Precipitations.After filtering
It collects filter cake and washs repeatedly, vacuum drying obtains crude product.Crude product is carried out column chromatography for separation purification, and (silica gel is to fix
Phase, CH2Cl2/ MeOH is eluent), obtain product.(1H NMR (500MHz, DMSO-d6): δ=8.09 (dd, 4H;Ar-H),
7.94ppm(dd,4H;Ar-H),7.71-7.51ppm(m,8H;Ar-H),7.40ppm(dd,4H;Ar-H),7.35ppm(dd,
4H;Ar-H),5.42ppm(s,Br,4H,OH),5.15ppm(s,2H;CH),4.45ppm(s,8H;Ar-CH2)。HRMS-ESI:
m/z:1014.2911(calcd.for[M+H]+,1014.2915)。)。
4) synthesis of four (2,2 '-two fluoro- 4- methylol azobenzene) ethane polyethers: to stirring, heating mantle and inside
Four (2,2 '-two fluoro- 4- methylol azobenzene) ethane 856g, 19.11g CHO are put into the 15L reaction kettle of water cooling coil pipe3Na
(0.2wt%) seals reaction kettle.Nitrogen is replaced three times, is opened stirring, is warming up to 100 DEG C and is dehydrated at -0.1MPa, so
After be warming up to 115 DEG C, be gently passed through propylene oxide, pass through control propylene oxide logical material speed keep reaction pressure <
0.4MPa, when be passed through propylene oxide amount to 8700g after stop charging, 115 DEG C progress aging reaction 5 hours;It cools the temperature to
It 90 DEG C, is neutralized with phosphoric acid, and carries out de- list at -0.1MPa, be cooled to room temperature to obtain four (2,2 '-two fluoro- 4- methylol azos
Benzene) ethane polyethenoxy ether (hydroxyl value: 24.9mg KOH/g, PDI:1.07, viscosity: 25 DEG C of 2811cP@).
Embodiment 3
1) the 3- methylaniline of 3kg, 1kg methanol the synthesis of four (3- toluidine) ethane: are added to 10L reaction kettle
In, it is 6 that hydrochloric acid regulation system pH, which is added, and nitrogen is replaced three times, and reaction temperature is 100 DEG C, and glyoxal is added using constant-flux pump
In reaction kettle, glyoxal 325g is added in coutroi velocity 5mL/min altogether.Charging finishes that the reaction was continued 10 hours, uses sodium bicarbonate
It is neutralized to neutrality, solvent under conditions of system temperature is 120 DEG C, vacuum degree -0.1Mpa in removing system, after removing solvent
Solution cooling obtain four (3- toluidine) ethane crude products.Crude product is carried out column chromatography for separation purification, and (silica gel is solid
Determine phase, CH2Cl2/ ethyl acetate is eluent), obtain product.
2) it the synthesis of 2- methyl -4- nitrosobenzene methanol: weighs the fluoro- 4- aminobenzene methanol of 2000g 2- and is dissolved in and fill
In the round-bottomed flask of 1000mL methylene chloride.The Oxone of 2.5 equivalents is dissolved in 1000mL distilled water.Under nitrogen protection,
Oxone solution is added drop-wise in round-bottomed flask, 6h is reacted at room temperature, there is Precipitation.It will be washed repeatedly, done with water after precipitating filtering
Dry acquisition crude product.
3) four (the 3- methylanilines of 1000g the synthesis of four (2,2 '-dimethyl -4- methylol azobenzene) ethane: are weighed
Base) the 2- methyl -4- nitrosobenzene methanol of ethane and 4.5 equivalents is dissolved in glacial acetic acid (AcOH) that volume ratio is 1:1 and DMSO is mixed
In bonding solvent.Under nitrogen protection, 60 DEG C of reaction 90h.After reaction, distilled water is added into system, there are a large amount of precipitating analysis
Out.Filter cake is collected after filtering and is washed repeatedly, and vacuum drying obtains crude product.Crude product is subjected to column chromatography for separation purification (silicon
Glue is stationary phase, CH2Cl2/ MeOH is eluent), obtain product.(1H NMR (500MHz, DMSO-d6): δ=8.19 (dd,
4H;Ar-H),8.04ppm(dd,4H;Ar-H),7.81ppm(d,4H;Ar-H),7.71ppm(d,4H;Ar-H),7.51ppm(d,
4H;Ar-H),7.41ppm(d,4H;Ar-H),5.32ppm(s,Br,4H,OH),5.05ppm(s,2H;CH),4.55ppm(s,
8H;Ar-CH2),1.55ppm(s,24H;CH3)。HRMS-ESI:m/z:982.4905(calcd.for[M+H]+,
982.4902)。)。
4) synthesis of four (2,2 '-dimethyl -4- methylol azobenzene) ethane polyethers: to stirring, heating mantle and interior
Four (2,2 '-dimethyl -4- methylol azobenzene) ethane 856g, 47.08g are put into the 15L reaction kettle of portion's water cooling coil pipe
CHO3K (0.5wt%) seals reaction kettle.Nitrogen is replaced three times, is opened stirring, is warming up to 100 DEG C and is taken off at -0.1MPa
Water then heats to 130 DEG C.Ethylene oxide and propylene oxide are mixed in head tank, EO/PO mass ratio is 60/40,
Then it is gently passed through ethylene oxide and propylene oxide mixture, reaction pressure < 0.4MPa is kept by control charging rate,
When be passed through ethylene oxide amount to 8560g after stop charging, 130 DEG C progress aging reaction 3 hours;90 DEG C are cooled the temperature to, is used
Lactic acid neutralizes, and de- list is carried out at -0.1MPa, is cooled to room temperature to obtain four (2,2 '-dimethyl -4- methylol azobenzene) ethane
Polyoxyethylene polyoxypropylene copolyether (hydroxyl value: 25.4mg KOH/g, PDI:1.08, viscosity: 25 DEG C of 2011cP@).
Application Example 1
Application of four (4- methylol azobenzene) the ethane polyethers in colouring art.
By 0.2wt% tetra- (4- methylol azobenzene) ethane polyethers (embodiment 1), 0.8%wt% lauryl sodium sulfate,
10% pigment printing paste, 5wt% acrylic ester adhesive and 84wt% deionized water are uniformly mixed and are configured to coloring agent, at room temperature
Uniform stirring generates uniform foam, and the blowing ratio for being is 14, and the foam of generation is coated in rapidly and knits by half-life period 6.3min
Object surface, and the fabric that Tu has coloring agent is put into baking oven rapidly and is dried, 80 DEG C of 10min have obtained color and have uniformly contaminated
Cloth.Residual foam can use 365nm ultraviolet light and vanish rapidly after dyeing, and half-life period is only 40s, recoverable.
Application Example 2
Application of four (4- methylol azobenzene) the ethane polyethers in crude oil demulsification field.
Demulsification test is carried out according to SY/T 5821-2000.The crude oil demulsifier sample of a certain amount of embodiment 1 is weighed, it is fixed
Amount is transferred in volumetric flask, is diluted to scale with ethyl alcohol, is shaken up, makes contained crude oil demulsifier quality in every 100m L solution
1g.Crude oil emulsion sample is put into the dehydration test bottle of 100m L and is heated to certain temperature, is added into dehydration test bottle
Four (4- methylol azobenzene) ethane polyethers of 100ppm.After screwing bottle cap, dehydration test bottle is placed in artificial oscillation case, water
Horizontal tremble is swung 50-200 times, after being sufficiently mixed uniformly, loosens bottle cap, and is placed in stand in water bath with thermostatic control by dehydration test bottle again and be sunk
Drop.The sewage quantity of different time abjection is estimated and records, respectively the ultra-violet absorption spectrum of test oil phase and water phase, analysis obtains water
Mutually and four (4- methylol azobenzene) ethane content of polyether in oily phase are 80ppm and 20ppm.