CN110396184B - Preparation method of isocyanurate polyether polyol - Google Patents
Preparation method of isocyanurate polyether polyol Download PDFInfo
- Publication number
- CN110396184B CN110396184B CN201910538500.3A CN201910538500A CN110396184B CN 110396184 B CN110396184 B CN 110396184B CN 201910538500 A CN201910538500 A CN 201910538500A CN 110396184 B CN110396184 B CN 110396184B
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- isocyanurate
- initiator
- epoxy compound
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of isocyanurate polyether polyol, which comprises the steps of S1, mixing an initiator tris (2-hydroxyethyl) isocyanurate with a catalyst to obtain an initial mixture; s2, dropwise adding an epoxy compound into the initial mixture, and heating to perform solid-liquid reaction to obtain a primary reaction product; s3, continuously adding an epoxy compound into the primary reaction product, and carrying out gas-liquid reaction to obtain a secondary reaction product; s4, cooling the secondary reaction product to obtain the isocyanurate polyether polyol; the temperature of the solid-liquid reaction is not more than 110 ℃, and the method avoids the color deepening of the final product due to local overheating by controlling the temperature of the solid-liquid reaction not to be more than 110 ℃, ensures that the reaction is safe and controllable, and reduces energy consumption and cost.
Description
Technical Field
The invention relates to the technical field of polyether polyol synthesis, in particular to a preparation method of isocyanurate polyether polyol.
Background
Ultraviolet (UV) curing is a material surface treatment technology, which utilizes the ultraviolet light to initiate the rapid polymerization and crosslinking of a liquid material with chemical activity, and instantly cures the liquid material into a solid material. The main components of the UV curing system comprise an oligomer, a monomer and a photoinitiator. The monomers, also known as reactive diluents or multifunctional acrylates, are an important component of UV-curing formulations, not only regulating the viscosity but also being film-forming substances, which have a significant influence on the final properties of the coating. Isocyanurate polyether polyols can be used in the preparation of UV curable monomers, which due to the particularity of their use, require isocyanurate polyether polyols having a lower color.
Chinese patent document CN106243339A discloses a preparation method of isocyanurate polyether polyol, firstly, an initiator of trihydroxyethyl isocyanurate is pretreated, then, the treated trihydroxyethyl isocyanurate and a double metal cyanide complex catalyst are added into a pressure-resistant reaction kettle, the temperature is raised to 130 +/-2 ℃, the vacuum pumping is carried out to-0.095 MPa, and nitrogen bubbling is carried out for 1 h; then adding alkylene oxide compound which accounts for 10-20% of the weight of the initiator to carry out initiation reaction, starting to continuously dropwise add the residual alkylene oxide compound to carry out continuous polymerization when the pressure of the reaction kettle is reduced to 0.01MPa, vacuumizing to remove the monomer for 1h after the reaction is finished, sampling to detect the hydroxyl value OHv of the isocyanurate polyether polyol, cooling, discharging and storing. The method can prepare the isocyanurate polyether polyol, but the method directly heats the solid initiator of the trihydroxyethyl isocyanurate and the catalyst to 130 +/-2 ℃ after mixing, because the melting point of the initiator of the trihydroxyethyl isocyanurate is 132-137 ℃, the solid is directly heated to 130 ℃, and the local overheating phenomenon can occur even under the stirring condition, thereby leading the chroma of the initiator and the final product to be deepened and failing to meet the raw material requirement of the UV curing monomer; in addition, the melting point of the initiator is not reached at 130 ℃, the solid initiator is not completely dissolved even if the local temperature may exceed 130 ℃, and at such a high temperature, 10-20% of the epoxy compound of the initiator is introduced at one time, so that the reaction is very violent, difficult to control and dangerous to some extent.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the prepared isocyanurate polyether polyol in the prior art has relatively deep chromaticity and cannot meet the requirement on the chromaticity of the monomer raw material in UV curing, so that the preparation method of the isocyanurate polyether polyol, which has the advantages of shallow chromaticity, capability of meeting the requirement on the chromaticity of the monomer raw material in UV curing, safe and easily controlled reaction, is provided.
To this end, the present invention provides a process for the preparation of an isocyanurate polyether polyol comprising,
s1, mixing an initiator tris (2-hydroxyethyl) isocyanurate with a catalyst to obtain an initial mixture;
s2, dropwise adding an epoxy compound into the initial mixture, and heating to perform solid-liquid reaction to obtain a primary reaction product;
s3, continuously adding an epoxy compound into the primary reaction product, and carrying out gas-liquid reaction to obtain a secondary reaction product;
s4, cooling the secondary reaction product to obtain the isocyanurate polyether polyol;
wherein the temperature of the solid-liquid reaction is not more than 110 ℃.
The preparation method of the isocyanurate polyether polyol comprises the step of preparing the isocyanurate polyether polyol by using an alkali metal catalyst, wherein the alkali metal catalyst comprises one or more of potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide, and the mass of the catalyst accounts for 0.03-3% of the mass of the isocyanurate polyether polyol, preferably 0.05-0.15%.
The preparation method of the isocyanurate polyether polyol comprises the step of adding acid after cooling the secondary reaction product in the step of S4, and stirring for 10-30 minutes, wherein the acid comprises one or two of acetic acid and lactic acid.
According to the preparation method of the isocyanurate polyether polyol, the epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin.
In the preparation method of the isocyanurate polyether polyol, in the step S1, after an initiator and a catalyst are mixed, nitrogen is introduced for replacement, so that the oxygen content is less than 100ppm, and preferably the oxygen content is less than 50 ppm.
In the preparation method of the isocyanurate polyether polyol, in the step S2, the amount of the dropwise added epoxy compound is 5-20% of the weight of the initiator, the temperature when the dropwise addition of the epoxy compound is started is 5-30 ℃, and stirring is carried out in the dropwise addition process.
In the preparation method of the isocyanurate polyether polyol, in the step S2, the amount of the dropwise added epoxy compound is 8-16% of the mass percent of the initiator.
In the preparation method of the isocyanurate polyether polyol, in the step S3, the gas-liquid reaction temperature is 110-150 ℃; in the S3 step and S4 step, the pressure of the solid-liquid reaction and the gas-liquid reaction is 0.60MPa or less, preferably 0.40MPa or less.
In the preparation method of the isocyanurate polyether polyol, in the step S4, the temperature of the secondary reaction product is reduced to 20-30 ℃.
The preparation method of the isocyanurate polyether polyol can set the proportion of the tris (2-hydroxyethyl) isocyanurate initiator to the total amount of the epoxy compound according to application requirements.
The technical scheme of the invention has the following advantages:
1. the preparation method of the isocyanurate polyether polyol comprises the steps of S1, mixing an initiator tris (2-hydroxyethyl) isocyanurate with a catalyst to obtain an initial mixture; s2, dropwise adding an epoxy compound into the initial mixture, and heating to perform solid-liquid reaction to obtain a primary reaction product; s3, continuously adding an epoxy compound into the primary reaction product, and carrying out gas-liquid reaction to obtain a secondary reaction product; s4, cooling the secondary reaction product to obtain the isocyanurate polyether polyol; the temperature of the solid-liquid reaction is not more than 110 ℃, the method comprises the steps of dropwise adding an epoxy compound into a mixture of an initiator and a catalyst at a lower temperature, slowly heating to perform the solid-liquid reaction, adding a certain amount of the epoxy compound in step S2, wherein the epoxy compound has certain solubility to the initiator, so that the solid initiator is favorably melted, and the initiator is melted more quickly along with the gradual increase of the temperature, so that the melting can be performed under the condition of being lower than the melting point of the initiator; the solid-liquid reaction temperature is controlled not to exceed 110 ℃, so that the initiator reacts while melting, the chroma deepening of the initiator and the final product caused by local overheating is avoided, and the final product can meet the chroma requirement of the UV curing monomer on the raw materials; and the solid-liquid reaction temperature is controlled in a lower range, so that the polymerization process is not particularly violent, the experiment is safer and more controllable, and the energy consumption and the cost are reduced.
2. The catalyst is an alkali metal catalyst and comprises one or more of potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide, the mass of the catalyst accounts for 0.03-3% of the mass of the isocyanurate polyether polyol, better catalytic effect can be ensured by adopting the alkali metal catalyst and controlling the addition amount of the alkali metal, and due to the fact that the tris (2-hydroxyethyl) isocyanurate has weak alkalinity, the pretreatment step of other catalysts (such as bimetallic catalysts) which can react in an acidic environment can be omitted by adopting the alkali metal catalyst, and experiments are simpler and more convenient.
3. In the step of S4, the preparation method of isocyanurate polyether polyol further comprises the step of adding acid after cooling the secondary reaction product, and stirring for 10-30 minutes, wherein the acid comprises one or two of acetic acid and lactic acid, and the alkali metal catalyst can be neutralized by adding the acid and stirring to obtain the qualified isocyanurate polyether polyol product.
4. According to the preparation method of the isocyanurate polyether polyol, the epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin, and the epoxy compound can be well subjected to polymerization reaction with the initiator tris (2-hydroxyethyl) isocyanurate to modify the initiator tris (2-hydroxyethyl) isocyanurate, so that the obtained isocyanurate polyether polyol has better UV curing performance after being esterified with acrylic acid.
5. In the preparation method of the isocyanurate polyether polyol, provided by the invention, in the step S1, after the initiator and the catalyst are mixed, nitrogen is introduced for replacement, so that the oxygen content is less than 100ppm, and residual air can be discharged by introducing nitrogen for replacement, thereby preventing the subsequently added epoxy compound from exploding when encountering oxygen.
6. In the preparation method of the isocyanurate polyether polyol provided by the invention, in the step S2, the amount of the dropwise added epoxy compound is 5-20% of the initiator by mass percent, the temperature when the dropwise addition of the epoxy compound is started is 5-30 ℃, stirring is carried out in the dropwise adding process, the amount of the epoxy compound dropwise added for the first time is controlled to be 5-20% of the initiator, if the added epoxy compound is too little (less than 5%), it does not act as a melting aid, and if it is added too much (more than 20%), it will cause the final product to have a non-uniform molecular weight distribution, the product will be cloudy, meanwhile, the phenomenon of overhigh pressure and potential safety hazard are caused, and by controlling the amount of the epoxy compound dripped for the first time, the chroma of the melted initiator and the chroma of the final product can be reduced, and the safety and controllability of the reaction can be ensured; the epoxy compound is dripped at a lower temperature of 5-30 ℃, so that the melting assisting effect on the initiator can be achieved, the phenomenon that the chroma of the initiator and the chroma of the final product are deepened due to local overheating can be avoided by continuously stirring in the dripping process, and the requirement of the UV curing monomer on the chroma of the raw material can be met by the final product.
7. According to the preparation method of the isocyanurate polyether polyol, provided by the invention, in the step S2, the amount of the dropwise added epoxy compound is 8-16% of the amount of the initiator by mass percent, and the chroma of the initiator after melting and the chroma of a final product can be better reduced by controlling the amount of the epoxy compound dropwise added for the first time to be 8-16% of the amount of the initiator, so that the final product meets the chroma requirement of a UV curing monomer on raw materials, and the safety and controllability of the reaction are ensured.
8. In the preparation method of the isocyanurate polyether polyol, provided by the invention, in the step S3, the gas-liquid reaction temperature is 110-150 ℃; in the steps S3 and S4, the pressure of the solid-liquid reaction and the gas-liquid reaction is less than or equal to 0.60Mpa, and the reaction is carried out at a lower reaction temperature by controlling the temperature of the gas-liquid reaction to be 110-150 ℃, so that the product chromaticity is prevented from being deepened due to overhigh temperature, and the energy consumption and the cost can be reduced.
9. In the preparation method of the isocyanurate polyether polyol, provided by the invention, in the step S4, the secondary reaction product is cooled to 20-30 ℃, and the final product can be kept at lower chroma by cooling the secondary reaction product to a lower temperature range, so that the chroma of the final product is prevented from being deepened, and the requirement of a UV curing monomer on the chroma of a raw material is met.
Detailed Description
Example 1
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, 550g of tris (2-hydroxyethyl) isocyanurate starter is mixed with 0.36g of potassium hydroxide catalyst, replaced by nitrogen and freed of residual air to an oxygen content of < 50ppm, giving an initial mixture.
S2, dropwise adding 27.5g of ethylene oxide (5 percent of the initiator) into the initial mixture at 15 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
And S3, adding 255.5g of ethylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 150 ℃, curing at the reaction temperature until the pressure does not drop, then adding 370g of propylene oxide to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 150 ℃, curing at the reaction temperature until the pressure does not drop, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 30 ℃, adding 0.39g of acetic acid, and stirring for 10 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 2
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, 596g of tris (2-hydroxyethyl) isocyanurate initiator is mixed with 0.6g of sodium hydroxide catalyst in a 2L reaction kettle, nitrogen is introduced for replacement, residual air in the kettle is removed, and the oxygen content is enabled to be less than 50ppm, so that an initial mixture is obtained.
S2, dripping 48g of ethylene oxide (8 percent of the initiator) into the initial mixture at the temperature of 20 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
S3, adding 556g of ethylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 120 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, then adding 370g of propylene oxide to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 120 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 1.35g of lactic acid, and stirring for 20 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 3
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, in a 2L reaction kettle, 550g of tris (2-hydroxyethyl) isocyanurate initiator is mixed with 1.8g of potassium methoxide catalyst, nitrogen is introduced for replacement, residual air in the kettle is removed, and the oxygen content is enabled to be less than 50ppm, so that an initial mixture is obtained.
S2, dropwise adding a mixture of 55g of ethylene oxide and propylene oxide (10% of the initiator) into the initial mixture at 30 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature not to exceed 110 ℃, controlling the pressure to be less than or equal to 0.40MPa, and obtaining a primary reaction product after the reaction is finished.
And S3, adding a mixture of 590g of ethylene oxide and propylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 120 ℃, curing at the reaction temperature until the pressure is not reduced, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 1.54g of acetic acid, and stirring for 30 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 4
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, in a 2L reaction kettle, 550g of tris (2-hydroxyethyl) isocyanurate initiator and 17.97g of potassium hydroxide catalyst are mixed, nitrogen is introduced for replacement, residual air in the kettle is removed, and the oxygen content is enabled to be less than 50ppm, so that an initial mixture is obtained.
S2, dripping 66g of propylene oxide (12 percent of the initiator) into the initial mixture at 10 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
S3, adding 302g of propylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, then adding 280g of ethylene oxide to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 25 ℃, adding 19.25g of acetic acid, and stirring for 15 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 5
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, in a 2L reaction kettle, 514g of tris (2-hydroxyethyl) isocyanurate initiator is mixed with 1.8g of sodium methoxide catalyst, nitrogen is introduced for replacement, residual air in the kettle is removed, and the oxygen content is enabled to be less than 50ppm, so that an initial mixture is obtained.
S2, dropwise adding 51g of propylene oxide (10% of the initiator) into the initial mixture at 25 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
And S3, adding 635g of propylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, curing at the reaction temperature until the pressure is not reduced, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 3g of lactic acid, and stirring for 15 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 6
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, 359g of tris (2-hydroxyethyl) isocyanurate initiator and 2.4g of potassium hydroxide catalyst are mixed in a 2L reaction kettle, nitrogen is introduced for replacement, residual air in the kettle is removed, and the oxygen content is enabled to be less than 50ppm, so that an initial mixture is obtained.
S2, dripping 57g of ethylene oxide (16 percent of the initiator) into the initial mixture at the temperature of 20 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
S3, adding 306g of ethylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, carrying out curing at the reaction temperature until the pressure does not drop, then adding 478g of propylene oxide to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, carrying out curing at the reaction temperature until the pressure does not drop, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 2.5g of acetic acid, and stirring for 15 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 7
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, mixing 660g of tris (2-hydroxyethyl) isocyanurate initiator and 2.4g of potassium hydroxide catalyst in a 2L reaction kettle, introducing nitrogen for replacement, and removing residual air in the kettle to ensure that the oxygen content is less than 50ppm to obtain an initial mixture.
S2, dropwise adding 52g of epoxy butane (8% of the initiator) into the initial mixture at 25 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
And S3, adding 488g of epoxybutane into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 110 ℃, curing at the reaction temperature until the pressure is not reduced, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 2.5g of acetic acid, and stirring for 15 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Example 8
This example provides a process for preparing an isocyanurate polyether polyol comprising,
s1, in a 2L reaction kettle, 492g of tris (2-hydroxyethyl) isocyanurate initiator and 36.9g of potassium hydroxide catalyst are mixed, nitrogen is introduced for replacement, and residual air in the kettle is removed to ensure that the oxygen content is less than 50ppm, so as to obtain an initial mixture.
S2, dripping 98.4g of ethylene oxide (20 percent of the initiator) into the initial mixture at the temperature of 5 ℃, slowly heating while carrying out solid-liquid reaction, gradually melting the initiator, controlling the solid-liquid reaction temperature to be not more than 110 ℃, and controlling the pressure to be not more than 0.40MPa, thus obtaining a primary reaction product after the reaction is finished.
S3, adding 151.6g of ethylene oxide into the primary reaction product to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 130 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, then adding 488g of butylene oxide to carry out gas-liquid reaction, controlling the gas-liquid reaction temperature to be 130 ℃, carrying out curing at the reaction temperature until the pressure does not decrease, and removing the residual epoxy compound in vacuum for 30min to obtain a secondary reaction product.
And S4, cooling the secondary reaction product to 20 ℃, adding 39.5g of acetic acid, and stirring for 15 minutes to obtain the isocyanurate polyether polyol.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Comparative example 1
This comparative example prepared isocyanurate polyether polyol by a method similar to that of example 5 except that in the step of S2, the temperature was raised to 130 ℃ before propylene oxide was added dropwise to the initial mixture, and a solid-liquid reaction was performed at this temperature; in the step S3, a gas-liquid reaction was carried out at 130 ℃.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Comparative example 2
This comparative example prepared isocyanurate polyether polyol by the same method as example 5 except that 1.54g of propylene oxide (3% of the initiator) was added dropwise to the initial mixture in the step of S2 and 684.46g of propylene oxide was added to the primary reaction product in the step of S3 to perform a gas-liquid reaction.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
Comparative example 3
This comparative example prepared isocyanurate polyether polyol by the same method as example 5 except that 154.2g of propylene oxide (30% of the initiator) was added dropwise to the initial mixture in the step of S2 and 531.8g of propylene oxide was added to the primary reaction product in the step of S3 to perform a gas-liquid reaction.
The appearance of the product was visually inspected and the color of the isocyanurate polyether polyol was measured with reference to GB/T3143 liquid chemical product color measurement and the results are shown in Table 1.
TABLE 1 results of color measurement of isocyanurate polyether polyol
| Product(s) | Appearance of the product | Chroma (Pt-Co) |
| Example 1 | Light yellow liquid | 30 |
| Example 2 | Light yellow liquid | 30 |
| Example 3 | Light yellow liquid | 30 |
| Example 4 | Light yellow liquid | 30 |
| Example 5 | Light yellow liquid | 30 |
| Example 6 | Light yellow liquid | 30 |
| Example 7 | Light yellow liquid | 30 |
| Example 8 | Light yellow liquid | 30 |
| Comparative example 1 | Yellow liquid | 150 |
| Comparative example 2 | Yellow liquid | 120 |
| Comparative example 3 | Pale yellow turbid liquid | 30 |
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A process for preparing an isocyanurate polyether polyol comprising,
s1, mixing an initiator tris (2-hydroxyethyl) isocyanurate with a catalyst to obtain an initial mixture;
s2, dropwise adding an epoxy compound into the initial mixture, and heating to perform solid-liquid reaction to obtain a primary reaction product;
s3, continuously adding an epoxy compound into the primary reaction product, and carrying out gas-liquid reaction to obtain a secondary reaction product;
s4, cooling the secondary reaction product to obtain the isocyanurate polyether polyol;
wherein the temperature of the solid-liquid reaction is not more than 110 ℃;
in the step S2, the amount of the dropwise added epoxy compound is 5-20% of the weight of the initiator, the temperature when the dropwise addition of the epoxy compound is started is 5-30 ℃, and stirring is carried out in the dropwise addition process.
2. The method according to claim 1, wherein the catalyst is an alkali metal catalyst, the alkali metal catalyst comprises one or more of potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide, and the mass of the catalyst is 0.03-3% of the mass of the isocyanurate polyether polyol.
3. The method of claim 2, wherein the step of S4 further comprises the step of adding an acid after cooling the secondary reaction product, and stirring for 10-30 minutes, wherein the acid comprises one or both of acetic acid and lactic acid.
4. The process for preparing isocyanurate polyether polyol of any of claims 1-3, wherein said epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin.
5. The process for producing isocyanurate polyether polyol as claimed in claim 1, wherein in the step S1, after mixing the initiator and the catalyst, nitrogen gas is introduced for replacement to make the oxygen content less than 100 ppm.
6. The process for producing isocyanurate polyether polyol as claimed in claim 1, wherein in the step of S2, the amount of the epoxy compound added dropwise is 8 to 16% by mass of the initiator.
7. The method for preparing isocyanurate polyether polyol as set forth in claim 1, wherein the temperature of the gas-liquid reaction in the S3 step is 110-150 ℃; in the S3 step and the S4 step, the pressure of the solid-liquid reaction and the gas-liquid reaction is less than or equal to 0.60 Mpa.
8. The process for producing isocyanurate polyether polyol as claimed in claim 3, wherein in the step of S4, said secondary reaction product is cooled to 20 to 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910538500.3A CN110396184B (en) | 2019-06-20 | 2019-06-20 | Preparation method of isocyanurate polyether polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910538500.3A CN110396184B (en) | 2019-06-20 | 2019-06-20 | Preparation method of isocyanurate polyether polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110396184A CN110396184A (en) | 2019-11-01 |
| CN110396184B true CN110396184B (en) | 2022-01-07 |
Family
ID=68323285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910538500.3A Active CN110396184B (en) | 2019-06-20 | 2019-06-20 | Preparation method of isocyanurate polyether polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110396184B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174040B (en) * | 2021-04-27 | 2022-05-17 | 杭州福斯特电子材料有限公司 | Photopolymerizable monomer and high-resolution high-adhesion LDI dry film resist composed of photopolymerizable monomer |
| CN115304762B (en) * | 2022-08-11 | 2023-12-29 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
| CN115353852B (en) * | 2022-09-23 | 2023-04-14 | 东莞华工佛塑新材料有限公司 | Yellowing-resistant transparent high-heat-resistance high-toughness polyurethane packaging adhesive for LED flexible light bar and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870716A (en) * | 1971-03-22 | 1975-03-11 | Allied Chem | Process for production of alkylene oxide adducts of iris(2-hydroxyalkyl)isocyanurate |
| CN106243339A (en) * | 2016-08-01 | 2016-12-21 | 山东诺威新材料有限公司 | Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent |
| CN106554494A (en) * | 2016-12-08 | 2017-04-05 | 陕西启源科技发展有限责任公司 | The preparation method of end-allyl group hyperbranched poly ethoxylated polyhydric alcohol |
| CN108129648A (en) * | 2016-12-01 | 2018-06-08 | 上海东大化学有限公司 | A kind of toluenediamine polyether polyol and preparation method thereof |
-
2019
- 2019-06-20 CN CN201910538500.3A patent/CN110396184B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870716A (en) * | 1971-03-22 | 1975-03-11 | Allied Chem | Process for production of alkylene oxide adducts of iris(2-hydroxyalkyl)isocyanurate |
| CN106243339A (en) * | 2016-08-01 | 2016-12-21 | 山东诺威新材料有限公司 | Isocyanuric acid ester polyether polyol and preparation method thereof and the preparation method of coating curing agent |
| CN108129648A (en) * | 2016-12-01 | 2018-06-08 | 上海东大化学有限公司 | A kind of toluenediamine polyether polyol and preparation method thereof |
| CN106554494A (en) * | 2016-12-08 | 2017-04-05 | 陕西启源科技发展有限责任公司 | The preparation method of end-allyl group hyperbranched poly ethoxylated polyhydric alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110396184A (en) | 2019-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110396184B (en) | Preparation method of isocyanurate polyether polyol | |
| WO2017156797A1 (en) | Method for circularly preparing polyether polyol by using dmc catalyst | |
| EP3129419B1 (en) | Method for the preparation of polyoxymethylene block copolymers | |
| CN112062945B (en) | High-functionality polyether polyol and preparation method thereof | |
| CN108070082B (en) | Method for preparing low-viscosity high-molecular-weight polyether polyol | |
| CN112225857A (en) | Isocyanurate-containing polyisocyanate composition with stable chromaticity and preparation method thereof | |
| DE2514127A1 (en) | PROCESS FOR PREPARING LOW MOLECULAR POLY-N-VINYLPYRROLIDONE-2 | |
| EP3898769B1 (en) | Product-to-product process for preparation of low viscosity polyoxyalkylene polyols | |
| CN111689859B (en) | Low-shrinkage resin and preparation method and application thereof | |
| CN106188312A (en) | A kind of production technology of 300 seconds degree nitrocottons | |
| CN110981778B (en) | Preparation method of cumyl peroxyneodecanoate and solvent-based CNP | |
| CN112029085A (en) | Method for preparing polyether polyol by adopting solution polymerization method | |
| CN113429557B (en) | Continuous preparation method of low-viscosity polyether polyol | |
| KR101606421B1 (en) | Process for preparing of acrylic water-swellable thickener by inverse emulsion polymerization | |
| CN112552503A (en) | Preparation method of bronopol reaction type flame-retardant polyether polyol | |
| CN101880383B (en) | Process for removing 1,4-dioxane in production process of high-carbon fatty alcohol polyoxyethylene ether | |
| CN103145983A (en) | Preparation method of bisphenol A type cyanate ester resin prepolymer | |
| KR101971738B1 (en) | Method for Preparation of Very Low Viscosity Hydroxylalkyl Cellulose with Partial Neutralization | |
| DE2500765C3 (en) | Process for reducing the content of monomeric vinyl chloride in polyvinyl chloride produced by bulk polymerization | |
| CN112011042A (en) | Preparation method of high molecular weight low viscosity polyether polyol | |
| CN115572385B (en) | Preparation method of plant-based polyether polyol | |
| US4177340A (en) | Manufacture of high-pressure polyethylene | |
| CN115850683B (en) | Preparation process of refined polyether suitable for textile auxiliary | |
| KR20240078756A (en) | Method of manufacturing ethylene vinyl alcohol copolymer | |
| JP4296364B2 (en) | Acrylic syrup manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |