CN110396184A - A kind of preparation method of isocyanuric acid ester polyether polyol - Google Patents
A kind of preparation method of isocyanuric acid ester polyether polyol Download PDFInfo
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- CN110396184A CN110396184A CN201910538500.3A CN201910538500A CN110396184A CN 110396184 A CN110396184 A CN 110396184A CN 201910538500 A CN201910538500 A CN 201910538500A CN 110396184 A CN110396184 A CN 110396184A
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- acid ester
- isocyanuric acid
- polyether polyol
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
Abstract
The present invention provides a kind of preparation methods of isocyanuric acid ester polyether polyol, including, initiator three (2- ethoxy) isocyanuric acid ester is mixed with catalyst S1, obtains original mixture；Epoxide is added dropwise in S2, Xiang Suoshu original mixture, heating carries out solid-liquid reaction, obtains primary first-order equation product；Epoxide is continuously added in S3, Xiang Suoshu primary first-order equation product, is carried out gas liquid reaction, is obtained secondary response product；S4, the secondary response product is cooled down, obtains the isocyanuric acid ester polyether polyol；Wherein, the temperature of the solid-liquid reaction is no more than 110 DEG C, and above method is no more than 110 DEG C by the temperature of control solid-liquid reaction, avoids the occurrence of hot-spot and final product coloration is caused to deepen, and to react safely controllable, reduces energy consumption and cost.
Description
Technical field
The present invention relates to polyether polyol synthesis technical fields, and in particular to a kind of system of isocyanuric acid ester polyether polyol
Preparation Method.
Background technique
Ultraviolet light (UV) solidification is a kind of surface treatment technology of material, it is using ultraviolet light-initiated with chemically active
The crosslinking of liquid material rapid polymerization, instantaneous solidification is at solid-state material, and compared with heat cure, UV solidification has VOC free release, saves
The features such as energy, high production efficiency.The main component of UV curing system includes oligomer, monomer and photoinitiator.List therein
Body is also known as active dilution or polyfunctional acrylic ester, is component part important in UV curing formula, it not only adjusts viscous
It spends and is film forming matter, the final performance of coating is had a significant impact.It is solid that isocyanuric acid ester polyether polyol can be used for UV
The preparation for changing monomer needs isocyanuric acid ester polyether polyol to have lower coloration due to the particularity of its application.
Chinese patent literature CN106243339A discloses a kind of preparation method of isocyanuric acid ester polyether polyol, first
Initiator tris(2-hydroxy ethyl)isocyanurate is pre-processed, it then will treated tris(2-hydroxy ethyl)isocyanurate and bimetallic
Cyanide complex catalyst is added in pressure-resistant reaction kettle, is warming up to 130 DEG C ± 2 DEG C, is evacuated to -0.095MPa, nitrogen drum
Steep 1h；Then the epoxyalkane compound that initiator weight 10%-20% is added carries out initiation reaction, under reactor pressure
When being down to 0.01MPa, starts the continuous residual epoxide alkane compound that is added dropwise and carry out continuous polymerization, vacuumize after reaction de- single
Body 1h, sample detection isocyanuric acid ester polyether polyol hydroxyl value OHv, cooling discharge save.Isocyanide can be prepared in this method
Urea acid esters polyether polyol, but this method is after mixing solid initiator tris(2-hydroxy ethyl)isocyanurate and catalyst, directly
It connects and is warming up to 130 DEG C ± 2 DEG C, since the fusing point of initiator tris(2-hydroxy ethyl)isocyanurate is 132-137 DEG C, directly heat solid
To 130 DEG C, the phenomenon that will appear hot-spot in the case of stirring, so as to cause initiator and final product coloration
It deepens, is unable to satisfy the ingredient requirement of UV curing monomer；In addition, 130 DEG C of fusing points for not reaching initiator, even if local temperature
It can exceed that 130 DEG C, solid initiator will not all dissolve, and at this high temperature, disposably be passed through initiator 10-20%
Epoxide, reaction can be very violent, it is difficult to control, have certain risk.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming the isocyanuric acid ester polyether being prepared in the prior art
Polyalcohol coloration is deeper, be unable to satisfy UV solidify in the defects of raw material monomer chromaticity requirements, thus provide it is a kind of obtain it is different
Cyanurate polyether polyol coloration is shallow, can satisfy UV solidify in requirement to raw material monomer coloration, and react easily-controllable safely
A kind of preparation method of isocyanuric acid ester polyether polyol of system.
For this purpose, the present invention provides a kind of preparation methods of isocyanuric acid ester polyether polyol, including,
S1, initiator three (2- ethoxy) isocyanuric acid ester is mixed with catalyst, obtains original mixture；
Epoxide is added dropwise in S2, Xiang Suoshu original mixture, heating carries out solid-liquid reaction, obtains primary first-order equation production
Object；
Epoxide is continuously added in S3, Xiang Suoshu primary first-order equation product, carries out gas liquid reaction, obtains secondary response production
Object；
S4, the secondary response product is cooled down, obtains the isocyanuric acid ester polyether polyol；
Wherein, the temperature of the solid-liquid reaction is no more than 110 DEG C.
The preparation method of the isocyanuric acid ester polyether polyol, the catalyst are base metal catalysts, including hydrogen
One or more of potassium oxide, sodium hydroxide, potassium methoxide, sodium methoxide, the quality of the catalyst account for the isocyanuric acid ester
The 0.03-3% of polyether polyol quality, preferably 0.05-0.15%.
The preparation method of the isocyanuric acid ester polyether polyol further includes producing the secondary response in S4 step
The step of acid is added after object cooling, and stirs 10-30 minutes, the acid includes one or both of acetic acid, lactic acid.
The preparation method of the isocyanuric acid ester polyether polyol, the epoxide are ethylene oxide, epoxy third
One or more of alkane, epoxy butane, epoxychloropropane.
The preparation method of the isocyanuric acid ester polyether polyol in S1 step, after initiator is mixed with catalyst, is led to
Nitrogen displacement, makes oxygen content < 100ppm, preferably oxygen content < 50ppm.
The preparation method of the isocyanuric acid ester polyether polyol, in S2 step, by percentage to the quality, the dropwise addition
Epoxide amount be the initiator 5-20%, start be added dropwise epoxide when temperature be 5-30 DEG C, be added dropwise
It is stirred in the process.
The preparation method of the isocyanuric acid ester polyether polyol, in S2 step, by percentage to the quality, the dropwise addition
Epoxide amount be the initiator 8-16%.
The preparation method of the isocyanuric acid ester polyether polyol, in S3 step, the temperature of the gas liquid reaction is
110-150℃；In S3 step and S4 step, the pressure of solid-liquid reaction and gas liquid reaction is≤0.60Mpa, preferably≤
0.40Mpa。
In S4 step, the secondary response product is cooled down for the preparation method of the isocyanuric acid ester polyether polyol
To 20-30 DEG C.
The preparation method of the isocyanuric acid ester polyether polyol can set three (2- hydroxyl second according to application demand
Base) isocyanuric acid ester initiator and epoxide total amount ratio.
Technical solution of the present invention has the advantages that
1. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, including, S1, by initiator three
(2- ethoxy) isocyanuric acid ester is mixed with catalyst, obtains original mixture；Epoxy is added dropwise in S2, Xiang Suoshu original mixture
Compound, heating carry out solid-liquid reaction, obtain primary first-order equation product；Epoxy is continuously added in S3, Xiang Suoshu primary first-order equation product
Compound carries out gas liquid reaction, obtains secondary response product；S4, the secondary response product is cooled down, obtains the isocyanide
Urea acid esters polyether polyol；Wherein, the temperature of the solid-liquid reaction is no more than 110 DEG C, and this method is in lower temperature, to starting
Epoxide is added dropwise in the mixture of agent and catalyst, then slowly heating, carry out solid-liquid reaction, in S2 step, first plus
Enter a certain amount of epoxide, since epoxide itself has certain dissolubility to initiator, facilitates solid starting
Agent melting, as temperature gradually rises, initiator is melted faster, may be implemented to carry out lower than initiator fusing point
Melting；Temperature by controlling solid-liquid reaction is no more than 110 DEG C, so that initiator is reacted in melting, avoids the occurrence of local mistake
Heat and cause initiator and final product coloration to deepen, so that final product is can satisfy UV curing monomer and the coloration of raw material wanted
It asks；And by the way that by the control of solid-liquid reaction temperature, in lower range, polymerization process will not especially acutely, so that more safety can for experiment
Control, while reducing energy consumption and cost.
2. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, the catalyst are urged for alkali metal
One or more of agent, including potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide, the quality of the catalyst account for described
The 0.03-3% of isocyanuric acid ester polyether polyol quality by using the above base metal catalysts, and controls alkali metal addition
Amount, it is ensured that preferable catalytic effect, and since isocyanuric acid ester is per se with alkalescent for three (2- ethoxys), by adopting
With the above base metal catalysts, other can be saved and need just to can be carried out the catalyst of reaction in acidic environment that (such as bimetallic is urged
Agent) pre-treatment step, make experiment it is easier.
3. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, in S4 step, further include, by institute
The step of acid is added after stating the cooling of secondary response product, and stirs 10-30 minutes, the acid includes one of acetic acid, lactic acid
Or two kinds, by the way that acid is added and stirs, base metal catalysts can be neutralized, obtain qualified isocyanuric acid ester polyether polyol
Product.
4. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, the epoxide is epoxy
One or more of ethane, propylene oxide, epoxy butane, epoxychloropropane can be compared with by using the above epoxide
Polymerization reaction is carried out with (2- ethoxy) isocyanuric acid ester of initiator three well, it is modified, thus the isocyanide made
After urea acid esters polyether polyol and acroleic acid esterification, there is better UV curing performance.
5. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, in S1 step, initiator with urge
After agent mixing, lead to nitrogen displacement, make oxygen content < 100ppm, by logical nitrogen displacement, residual air can be discharged, be prevented
The epoxide of subsequent addition encounters oxygen and explodes.
6. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, in S2 step, with quality percentage
Than meter, the amount of the epoxide of the dropwise addition is the 5-20% of the initiator, starts to be added dropwise temperature when epoxide
It is 5-30 DEG C, is stirred during being added dropwise, the amount for the epoxide that control is added dropwise for the first time is the 5-20% of initiator, if
The epoxide of addition is very few (being less than 5%), then does not have the effect for helping and melting, and addition is excessive (being more than 20%), it will cause
Final product molecular weight distribution is uneven, and product can be muddy, while will cause hypertonia phenomenon, causes security risk, passes through control
System for the first time be added dropwise epoxide amount, can reduce initiator melting after coloration and final products coloration it is same
When, guarantee the safely controllable of reaction；By starting at 5-30 DEG C of lower temperature that epoxide is added dropwise, can play to rising
Effect is melted in helping for beginning agent, by being stirred continuously during dropwise addition, can be avoided the occurrence of hot-spot and be led to initiator and most
Final product coloration deepens, and guarantees that final product can satisfy UV curing monomer to the chromaticity requirements of raw material.
7. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, in S2 step, with quality percentage
Than meter, the amount of the epoxide of the dropwise addition is the 8-16% of the initiator, the epoxidation being added dropwise for the first time by control
The amount for closing object is the 8-16% of initiator, the coloration of coloration and final products after can preferably reducing initiator melting,
So that final product is met UV curing monomer to the chromaticity requirements of raw material, while guaranteeing the safely controllable of reaction.
8. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention, in S3 step, the gas-liquid is anti-
The temperature answered is 110-150 DEG C；In S3 step and S4 step, the pressure of solid-liquid reaction and gas liquid reaction is≤0.60Mpa, is passed through
The temperature for controlling gas liquid reaction is 110-150 DEG C, reacts reaction under lower reaction temperature, on the one hand avoids temperature
It is excessively high and make product coloration deepen, on the other hand can reduce energy consumption and cost.
It, will be described secondary in S4 step 9. a kind of preparation method of isocyanuric acid ester polyether polyol provided by the invention
Reaction product is cooled to 20-30 DEG C, by the way that secondary response product is cooled to lower temperature range, can make final product
It is maintained at lower coloration, prevents its coloration from deepening, meets UV curing monomer to the chromaticity requirements of raw material.
Specific embodiment
Embodiment 1
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1,550g tri- (2- ethoxy) isocyanuric acid ester initiator is mixed with 0.36g potassium hydroxide catalyst, leads to nitrogen
Displacement excludes residual air, makes oxygen content < 50ppm, obtain original mixture.
S2,27.5g ethylene oxide (the 5% of initiator) is added dropwise into original mixture at 15 DEG C, side is slowly heated up, side
Solid-liquid reaction is carried out, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa,
End of reaction obtains primary first-order equation product.
S3, the progress gas liquid reaction of 255.5g ethylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is
It 150 DEG C, is cured to pressure under reaction temperature and is not dropped, 370g propylene oxide is then added, carry out gas liquid reaction, control gas-liquid
Reaction temperature is 150 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min is obtained
Secondary response product.
S4, secondary response product is cooled to 30 DEG C, 0.39g acetic acid is added, stirred 10 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 2
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, (2- ethoxy) the isocyanuric acid ester initiator of 596g tri- and 0.6g is sodium hydroxide catalyzed
Agent mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,48g ethylene oxide (the 8% of initiator) is added dropwise into original mixture at 20 DEG C, side is slowly heated up, Bian Jin
Row solid-liquid reaction, initiator gradually melt, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa, instead
It should finish to obtain primary first-order equation product.
S3, the progress gas liquid reaction of 556g ethylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is 120
DEG C, it is cured under reaction temperature to pressure and is not dropped, 370g propylene oxide is then added, carry out gas liquid reaction, control gas-liquid is anti-
Answering temperature is 120 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min obtains two
Secondary response product.
S4, secondary response product is cooled to 20 DEG C, 1.35g lactic acid is added, stirred 20 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 3
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, by (2- ethoxy) the isocyanuric acid ester initiator of 550g tri- and 1.8g potassium methoxide catalyst
Mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2, at 30 DEG C into original mixture be added dropwise 55g ethylene oxide, propylene oxide mixture (initiator
10%), side is slowly heated up, and Bian Jinhang solid-liquid reaction, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, control
Pressing pressure is≤0.40MPa, and end of reaction obtains primary first-order equation product.
S3, the mixture progress gas liquid reaction that 590g ethylene oxide, propylene oxide are added into primary first-order equation product, control
Gas liquid reaction temperature is 120 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min,
Obtain secondary response product.
S4, secondary response product is cooled to 20 DEG C, 1.54g acetic acid is added, stirred 30 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 4
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, (2- ethoxy) the isocyanuric acid ester initiator of 550g tri- is urged with 17.97g potassium hydroxide
Agent mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,66g propylene oxide (the 12% of initiator) is added dropwise into original mixture at 10 DEG C, side is slowly heated up, side
Solid-liquid reaction is carried out, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa,
End of reaction obtains primary first-order equation product.
S3, the progress gas liquid reaction of 302g propylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is 110
DEG C, it is cured under reaction temperature to pressure and is not dropped, 280g ethylene oxide is then added, carry out gas liquid reaction, control gas-liquid is anti-
Answering temperature is 110 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min obtains two
Secondary response product.
S4, secondary response product is cooled to 25 DEG C, 19.25g acetic acid is added, stirred 15 minutes, obtain isocyanuric acid ester
Polyether polyol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 5
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, by (2- ethoxy) the isocyanuric acid ester initiator of 514g tri- and 1.8g sodium methoxide catalyst
Mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,51g propylene oxide (the 10% of initiator) is added dropwise into original mixture at 25 DEG C, side is slowly heated up, side
Solid-liquid reaction is carried out, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa,
End of reaction obtains primary first-order equation product.
S3, the progress gas liquid reaction of 635g propylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is 110
DEG C, it is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min obtains secondary response product.
S4, secondary response product is cooled to 20 DEG C, 3g lactic acid is added, stirred 15 minutes, obtain isocyanuric acid ester polyether
Polyalcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 6
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, by (2- ethoxy) the isocyanuric acid ester initiator of 359g tri- and 2.4g potassium hydroxide catalysed
Agent mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,57g ethylene oxide (the 16% of initiator) is added dropwise into original mixture at 20 DEG C, side is slowly heated up, side
Solid-liquid reaction is carried out, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa,
End of reaction obtains primary first-order equation product.
S3, the progress gas liquid reaction of 306g ethylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is 110
DEG C, it is cured under reaction temperature to pressure and is not dropped, 478g propylene oxide is then added, carry out gas liquid reaction, control gas-liquid is anti-
Answering temperature is 110 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min obtains two
Secondary response product.
S4, secondary response product is cooled to 20 DEG C, 2.5g acetic acid is added, stirred 15 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 7
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, by (2- ethoxy) the isocyanuric acid ester initiator of 660g tri- and 2.4g potassium hydroxide catalysed
Agent mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,52g epoxy butane (the 8% of initiator) is added dropwise into original mixture at 25 DEG C, side is slowly heated up, Bian Jin
Row solid-liquid reaction, initiator gradually melt, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa, instead
It should finish to obtain primary first-order equation product.
S3, the progress gas liquid reaction of 488g epoxy butane is added into primary first-order equation product, control gas liquid reaction temperature is 110
DEG C, it is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min obtains secondary response product.
S4, secondary response product is cooled to 20 DEG C, 2.5g acetic acid is added, stirred 15 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Embodiment 8
A kind of preparation method of isocyanuric acid ester polyether polyol is present embodiments provided, including,
S1, in 2L reaction kettle, by (2- ethoxy) the isocyanuric acid ester initiator of 492g tri- and 36.9g potassium hydroxide catalysed
Agent mixing leads to nitrogen displacement, excludes residual air in kettle, make oxygen content < 50ppm, obtain original mixture.
S2,98.4g ethylene oxide (the 20% of initiator) is added dropwise into original mixture at 5 DEG C, side is slowly heated up, side
Solid-liquid reaction is carried out, initiator gradually melts, and control solid-liquid reaction temperature is no more than 110 DEG C, and control pressure is≤0.40MPa,
End of reaction obtains primary first-order equation product.
S3, the progress gas liquid reaction of 151.6g ethylene oxide is added into primary first-order equation product, control gas liquid reaction temperature is
It 130 DEG C, is cured to pressure under reaction temperature and is not dropped, 488g epoxy butane is then added, carry out gas liquid reaction, control gas-liquid
Reaction temperature is 130 DEG C, is cured under reaction temperature to pressure and is not dropped, vacuum removal residual epoxy compound 30min is obtained
Secondary response product.
S4, secondary response product is cooled to 20 DEG C, 39.5g acetic acid is added, stirred 15 minutes, it is poly- to obtain isocyanuric acid ester
Ethoxylated polyhydric alcohol.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Comparative example 1
This comparative example prepares isocyanuric acid ester polyether polyol using method similar to Example 5, the difference is that,
In S2 step, before propylene oxide is added dropwise into original mixture, 130 DEG C is first raised the temperature to, is consolidated at such a temperature
Liquid reaction；In S3 step, gas liquid reaction is carried out at 130 DEG C.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Comparative example 2
This comparative example prepares isocyanuric acid ester polyether polyol using method similar to Example 5, the difference is that,
In S2 step, 1.54g propylene oxide (the 3% of initiator) is added dropwise into original mixture, in S3 step, to primary first-order equation product
Middle addition 684.46g propylene oxide carries out gas liquid reaction.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
Comparative example 3
This comparative example prepares isocyanuric acid ester polyether polyol using method similar to Example 5, the difference is that,
In S2 step, 154.2g propylene oxide (the 30% of initiator) is added dropwise into original mixture, in S3 step, is produced to primary first-order equation
531.8g propylene oxide is added in object and carries out gas liquid reaction.
The appearance of product is estimated, and refers to GB/T3143 liquid chemical product colour measurement method, detection isocyanuric acid ester is poly-
The coloration of ethoxylated polyhydric alcohol, what is obtained the results are shown in Table 1.
The colorimetric detection result of 1 isocyanuric acid ester polyether polyol of table
| Product | Appearance | Coloration (Pt-Co) |
| Embodiment 1 | Weak yellow liquid | 30 |
| Embodiment 2 | Weak yellow liquid | 30 |
| Embodiment 3 | Weak yellow liquid | 30 |
| Embodiment 4 | Weak yellow liquid | 30 |
| Embodiment 5 | Weak yellow liquid | 30 |
| Embodiment 6 | Weak yellow liquid | 30 |
| Embodiment 7 | Weak yellow liquid | 30 |
| Embodiment 8 | Weak yellow liquid | 30 |
| Comparative example 1 | Yellow liquid | 150 |
| Comparative example 2 | Yellow liquid | 120 |
| Comparative example 3 | Faint yellow troubled liquor | 30 |
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of preparation method of isocyanuric acid ester polyether polyol, which is characterized in that including,
S1, initiator three (2- ethoxy) isocyanuric acid ester is mixed with catalyst, obtains original mixture；
Epoxide is added dropwise in S2, Xiang Suoshu original mixture, heating carries out solid-liquid reaction, obtains primary first-order equation product；
Epoxide is continuously added in S3, Xiang Suoshu primary first-order equation product, is carried out gas liquid reaction, is obtained secondary response product；
S4, the secondary response product is cooled down, obtains the isocyanuric acid ester polyether polyol；
Wherein, the temperature of the solid-liquid reaction is no more than 110 DEG C.
2. the preparation method of isocyanuric acid ester polyether polyol according to claim 1, which is characterized in that the catalyst
For one or more of base metal catalysts, including potassium hydroxide, sodium hydroxide, potassium methoxide, sodium methoxide, the catalyst
Quality accounts for the 0.03-3% of the isocyanuric acid ester polyether polyol quality.
3. the preparation method of isocyanuric acid ester polyether polyol according to claim 2, which is characterized in that in S4 step,
It further include that the step of acid will be added after secondary response product cooling, and stir 10-30 minutes, the acid includes acetic acid, cream
One or both of acid.
4. the preparation method of isocyanuric acid ester polyether polyol according to claim 1 to 3, which is characterized in that described
Epoxide is one or more of ethylene oxide, propylene oxide, epoxy butane, epoxychloropropane.
5. the preparation method of isocyanuric acid ester polyether polyol according to claim 1 to 4, which is characterized in that S1 step
In rapid, after initiator is mixed with catalyst, lead to nitrogen displacement, make oxygen content < 100ppm.
6. the preparation method of -5 any isocyanuric acid ester polyether polyol according to claim 1, which is characterized in that S2 step
In rapid, by percentage to the quality, the amount of the epoxide of the dropwise addition is the 5-20% of the initiator, starts that epoxy is added dropwise
Temperature when compound is 5-30 DEG C, is stirred during being added dropwise.
7. the preparation method of isocyanuric acid ester polyether polyol according to claim 6, which is characterized in that in S2 step,
By percentage to the quality, the amount of the epoxide of the dropwise addition is the 8-16% of the initiator.
8. the preparation method of -7 any isocyanuric acid ester polyether polyol according to claim 1, which is characterized in that S3 step
In rapid, the temperature of the gas liquid reaction is 110-150 DEG C；In S3 step and S4 step, the pressure of solid-liquid reaction and gas liquid reaction
For≤0.60Mpa.
9. the preparation method of -8 any isocyanuric acid ester polyether polyol according to claim 1, which is characterized in that S4 step
In rapid, the secondary response product is cooled to 20-30 DEG C.
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| CN115304762A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
| CN115353852A (en) * | 2022-09-23 | 2022-11-18 | 东莞华工佛塑新材料有限公司 | Yellowing-resistant transparent high-heat-resistant high-toughness polyurethane packaging adhesive for LED flexible light bar and preparation method thereof |
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