CN110938202A - Preparation method of Mannich flame-retardant polyether polyol - Google Patents
Preparation method of Mannich flame-retardant polyether polyol Download PDFInfo
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- CN110938202A CN110938202A CN201911308859.8A CN201911308859A CN110938202A CN 110938202 A CN110938202 A CN 110938202A CN 201911308859 A CN201911308859 A CN 201911308859A CN 110938202 A CN110938202 A CN 110938202A
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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
- C08G65/2639—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 elements other than oxygen, nitrogen or sulfur
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of preparation of flame-retardant polyether polyol, and particularly relates to a preparation method of Mannich flame-retardant polyether polyol. The method comprises the steps of adopting an aromatic phenol compound, paraformaldehyde or a formaldehyde aqueous solution to react with diethanol amine to prepare Mannich base, reacting the Mannich base with phosphorus oxychloride to generate a chlorine and phosphorus element modified Mannich base initiator, simultaneously controlling the proportion and the feeding mode of the phosphorus oxychloride, modifying Mannich base molecules through phosphorus oxychloride groups to synthesize a macromolecular Mannich base initiator with higher functionality, and finally carrying out polymerization reaction on the macromolecular Mannich base initiator and alkane oxide to obtain the special Mannich flame-retardant polyether polyol.
Description
Technical Field
The invention belongs to the technical field of preparation of flame-retardant polyether polyol, and particularly relates to a preparation method of Mannich flame-retardant polyether polyol.
Background
The Mannich reaction is an organic chemical reaction in which a compound containing active hydrogen is condensed with formaldehyde and secondary amine or ammonia to generate β -amino compound, can combine a plurality of flame retardant elements together, and can be widely applied to rigid polyurethane foams, semi-rigid polyurethane foams and even soft polyurethane foams.
Meanwhile, the Mannich base has hydroxyl and certain autocatalysis activity, and can further perform polymerization reaction with alkylene oxide to finally obtain the reactive flame-retardant polyether polyol. Compared with an additive flame retardant, the reactive flame retardant polyether exists in a cross-linked network of the polyurethane foam material in a chemical bond form, so that the migration problem does not exist, and the mechanical property of the material cannot be obviously influenced when the reactive flame retardant polyether is added in a large amount.
Fyrol-6 is a classic example of a flame retardant for polyurethane production using a Mannich reaction, and companies such as Acksoll, Strofu, etc. are the first researchers and producers of this product. The conventional Mannich polyether polyol product applied to the market at present has the problems of poor flame retardant effect, foam strength, fluidity and the like when being used for polyurethane rigid foam, and incapability of combining flame retardance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, and provides a method for preparing Mannich flame-retardant polyether polyol. The polyurethane foam prepared from the flame-retardant polyether polyol has excellent temperature resistance and fire resistance, achieves the effect of permanent flame retardance, and has wide application prospect.
The preparation method of the Mannich flame-retardant polyether polyol specifically comprises the following steps:
(1) preparation of mannich base: putting an aromatic phenolic compound, an aldehyde substance, diethanolamine and a catalyst into a reaction kettle, heating to 60-100 ℃ for reaction for 2-4h to obtain Mannich base;
(2) preparing a macromolecular Mannich base intermediate containing chlorine and phosphorus elements: reducing the temperature of the Mannich base prepared in the step (1) to 0-20 ℃, then dropwise adding phosphorus oxychloride to start reaction, starting a vacuum pump, pumping HCl gas generated by the reaction, controlling cooling water, keeping the temperature in the reaction kettle not more than 35 ℃, and after the dropwise addition of the phosphorus oxychloride is finished, raising the temperature to 30-70 ℃ to react for 2-4 hours;
(3) high-temperature polymerization: and (3) adding a polymerization reaction catalyst into the reaction kettle of the macromolecular Mannich base intermediate containing chlorine and phosphorus prepared in the step (2), heating to 100 ℃ and 130 ℃, dropwise adding a polymerization monomer, keeping the pressure in the kettle at 0.1-0.5MPa, sampling after curing, testing the monomer content in polyether, and vacuumizing to remove unreacted monomers to obtain the Mannich flame-retardant polyether polyol.
The aromatic phenolic compound in the step (1) is one or more of bisphenol A, cardanol, phenol or nonyl phenol.
The aldehyde substance in the step (1) is one or more of paraformaldehyde, formaldehyde, acetaldehyde or propionaldehyde.
The molar ratio of the aromatic phenolic compound, the aldehyde substance and the diethanol amine in the step (1) is 0.2-1:0.1-4: 0.1-5.
The mol ratio of the Mannich base to the phosphorus oxychloride in the step (2) is 0.2-1: 0.1-2.
The catalyst in the step (1) and the step (3) is a macromolecular tertiary amine catalyst. The Mannich base reaction catalyst is preferably selected, the yield of the Mannich base can be greatly improved, and meanwhile, the catalyst can also be used for the polymerization reaction of the Mannich base and an olefin oxide monomer, so that the comprehensive effect is better.
The polymerized monomer in the step (3) is one or more of propylene oxide, epichlorohydrin or ethylene oxide.
According to the invention, through the formula and process design, phosphorus oxychloride is introduced into a Mannich base structure, so that a very beneficial effect can be produced on the improvement of the flame retardance of a product, meanwhile, the proportion and the feeding mode of the phosphorus oxychloride are controlled, Mannich base molecules are combined into macromolecular Mannich base through phosphorus oxychloride groups, and a macromolecular Mannich base initiator with higher functionality is synthesized; the Mannich polyether polyol prepared by the invention has benzene rings, nitrogen elements, phosphorus elements and chlorine elements, and has a high-efficiency synergistic flame-retardant effect; the polyurethane foam prepared from the flame-retardant polyether polyol has excellent temperature resistance and fire resistance, achieves the effect of permanent flame retardance, and has wide application prospect.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of Mannich flame-retardant polyether polyol, which is characterized in that active hydroxyl of Mannich base is connected with phosphorus oxychloride groups, so that efficient synergistic flame retardance of benzene ring, nitrogen element, phosphorus element and chlorine element is achieved, and the flame-retardant effect of the product is effectively improved; according to the invention, through effectively controlling the feeding mode and the feeding proportion of phosphorus oxychloride, the Mannich base is combined into the macromolecular Mannich base through the bridge action of the phosphorus oxychloride, so that the functionality of the product is improved, the prepared polyurethane rigid foam has better strength, and the flame retardance of the product can be further improved.
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials used in the examples are all commercially available unless otherwise specified.
Example 1
(1) Preparation of mannich base: 228g of bisphenol A, 420g of diethanolamine and 324g of 37% formaldehyde aqueous solution are added into a reaction kettle provided with a stirrer, a thermometer, a condensing device and a nitrogen protection device, and 6g of 2,4, 6-tris (dimethylaminomethyl) phenol is added at the same time, and the reaction is carried out for 3 hours at 80 ℃;
(2) preparation of macromolecular mannich base intermediate: the temperature of the Mannich base is reduced to 5 ℃, 77g of phosphorus oxychloride is slowly dripped into a reaction kettle in a stirring state for 1 hour, a vacuum pump is started, HCl gas generated by the reaction is timely pumped out, cooling water is controlled, the temperature in the reaction kettle is not more than 35 ℃, and the temperature is raised to 60 ℃ after the phosphorus oxychloride is completely pumped in, and the reaction is carried out for 3 hours.
(3) Preparation of flame-retardant mannich polyether: heating the reaction kettle to 100 ℃, vacuumizing, bubbling nitrogen, completely removing water in the Mannich base, keeping the reaction temperature at 100 ℃ after dehydration is finished, slowly dripping 384g of propylene oxide into the reaction kettle for 3 hours, curing and reacting for 2 hours, and finally removing monomers in vacuum to obtain the Mannich polyether polyol.
Example 2
(1) Preparation of mannich base: 228g of bisphenol A, 420g of diethanolamine and 324g of 37% formaldehyde aqueous solution are added into a reaction kettle provided with a stirrer, a thermometer, a condensing device and a nitrogen protection device, and 6g of 2,4, 6-tris (dimethylaminomethyl) phenol is added at the same time, and the reaction is carried out for 3 hours at 80 ℃;
(2) preparation of macromolecular mannich base intermediate: reducing the temperature of the Mannich base to 0 ℃, slowly dripping 38.5g of phosphorus oxychloride into the reaction kettle in a stirring state for 2 hours, starting a vacuum pump, timely pumping out HCl gas generated by the reaction, controlling cooling water to ensure that the temperature in the reaction kettle does not exceed 35 ℃, and increasing the temperature to 50 ℃ after the phosphorus oxychloride is completely pumped in, and reacting for 3 hours;
(3) preparation of flame-retardant mannich polyether: heating the reaction kettle to 100 ℃, vacuumizing, bubbling nitrogen, completely removing water in the Mannich base, keeping the reaction temperature at 100 ℃ after dehydration is finished, slowly dripping 467g of propylene oxide into the reaction kettle for 3 hours, curing and reacting for 2 hours, and finally removing monomers in vacuum to obtain the Mannich polyether polyol.
Example 3
(1) Preparation of mannich base: adding 300g of cardanol, 420g of diethanolamine and 324g of 37% formaldehyde aqueous solution into a reaction kettle provided with a stirrer, a thermometer, a condensing device and a nitrogen protection device, simultaneously adding 6g of 2,4, 6-tris (dimethylaminomethyl) phenol, and reacting for 3 hours at 80 ℃;
(2) preparation of macromolecular mannich base intermediate: reducing the temperature of the Mannich base to 10 ℃, slowly dripping 77g of phosphorus oxychloride into the reaction kettle in a stirring state for 0.5h, starting a vacuum pump, timely pumping out HCl gas generated by the reaction, controlling cooling water to ensure that the temperature in the reaction kettle does not exceed 35 ℃, and increasing the temperature to 70 ℃ after the phosphorus oxychloride is completely pumped in, and reacting for 3 h;
(3) preparation of flame-retardant mannich polyether: and heating the reaction kettle to 100 ℃, vacuumizing, and bubbling nitrogen to completely remove the water in the Mannich base. And after the dehydration is finished, keeping the reaction temperature at 100 ℃, slowly dripping 330g of propylene oxide into the reaction kettle for 4 hours, curing and reacting for 2 hours, and finally removing the monomer in vacuum to obtain the Mannich polyether polyol.
Comparative example 1
(1) Preparation of mannich base: 228g of bisphenol A, 420g of diethanolamine and 324g of 37% formaldehyde aqueous solution were added to a reaction vessel equipped with a stirrer, a thermometer, a condensing device and a nitrogen gas guard, and 6g of 2,4, 6-tris (dimethylaminomethyl) phenol was added at the same time, and the reaction was carried out at 80 ℃ for 3 hours.
(2) Preparation of mannich polyether: and heating the reaction kettle to 100 ℃, vacuumizing, and bubbling nitrogen to completely remove the water in the Mannich base. After the dehydration is finished, keeping the reaction temperature at 100 ℃, slowly dripping 550g of propylene oxide into the reaction kettle for 3 hours, curing and reacting for 2 hours, and finally removing the monomer in vacuum to obtain the Mannich polyether polyol.
And (3) performance test, synthesizing polyether products by using the polyether polyols prepared in the examples 1-3 and the comparative example 1 under the same conditions, and simultaneously performing performance test under the same test conditions, wherein the test data results are shown in table 1.
TABLE 1 polyether product Performance data for examples 1-3 and comparative example 1
| Product index | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Hydroxyl value, mgKOH/g | 453 | 448 | 446 | 452 |
| Viscosity, mPa.s/25 deg.C | 20100 | 14000 | 13500 | 12000 |
| Oxygen index | 26.7 | 25.4 | 26.1 | 24.3 |
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A preparation method of Mannich flame-retardant polyether polyol is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of mannich base: putting an aromatic phenolic compound, an aldehyde substance, diethanolamine and a catalyst into a reaction kettle, heating to 60-100 ℃ for reaction to obtain Mannich base;
(2) preparing a macromolecular Mannich base intermediate containing chlorine and phosphorus elements: reducing the temperature of the Mannich base prepared in the step (1) to 0-20 ℃, then dropwise adding phosphorus oxychloride to start reaction, after the dropwise adding of the phosphorus oxychloride is finished, raising the temperature to 30-70 ℃, and reacting for 2-4 h;
(3) high-temperature polymerization: and (3) adding a polymerization reaction catalyst into the reaction kettle of the macromolecular Mannich base intermediate containing chlorine and phosphorus prepared in the step (2), heating to 100 ℃ and 130 ℃, dropwise adding a polymerization monomer, keeping the pressure in the kettle at 0.1-0.5MPa, and obtaining the Mannich flame-retardant polyether polyol after curing.
2. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the aromatic phenolic compound in the step (1) is one or more of bisphenol A, cardanol, phenol or nonyl phenol.
3. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the aldehyde substance in the step (1) is one or more of paraformaldehyde, formaldehyde, acetaldehyde or propionaldehyde.
4. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the molar ratio of the aromatic phenolic compound, the aldehyde substance and the diethanol amine in the step (1) is 0.2-1:0.1-4: 0.1-5.
5. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the mol ratio of the Mannich base to the phosphorus oxychloride in the step (2) is 0.2-1: 0.1-2.
6. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the catalyst in the step (1) and the step (3) is a macromolecular tertiary amine catalyst.
7. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the polymerized monomer in the step (3) is one or more of propylene oxide, epichlorohydrin or ethylene oxide.
8. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: dropwise adding phosphorus oxychloride in the step (2) to start reaction, starting a vacuum pump, pumping HCl gas generated by the reaction, controlling cooling water, and keeping the temperature in the reaction kettle not to exceed 35 ℃.
9. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: and (3) sampling to test the monomer content in the polyether after the curing is finished, and then vacuumizing to remove unreacted monomers to obtain the Mannich flame-retardant polyether polyol.
10. The method of preparing a mannich flame retardant polyether polyol according to claim 1, characterized in that: the method comprises the following steps:
(1) preparation of mannich base: putting an aromatic phenolic compound, an aldehyde substance, diethanolamine and a catalyst into a reaction kettle, heating to 60-100 ℃ for reaction for 2-4h to obtain Mannich base;
(2) preparing a macromolecular Mannich base intermediate containing chlorine and phosphorus elements: reducing the temperature of the Mannich base prepared in the step (1) to 0-20 ℃, then dropwise adding phosphorus oxychloride to start reaction, starting a vacuum pump, pumping HCl gas generated by the reaction, controlling cooling water, keeping the temperature in the reaction kettle not more than 35 ℃, and after the dropwise addition of the phosphorus oxychloride is finished, raising the temperature to 30-70 ℃ to react for 2-4 hours;
(3) high-temperature polymerization: and (3) adding a polymerization reaction catalyst into the reaction kettle of the macromolecular Mannich base intermediate containing chlorine and phosphorus prepared in the step (2), heating to 100 ℃ and 130 ℃, dropwise adding a polymerization monomer, keeping the pressure in the kettle at 0.1-0.5MPa, sampling after curing, testing the monomer content in polyether, and vacuumizing to remove unreacted monomers to obtain the Mannich flame-retardant polyether polyol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250858A (en) * | 2020-08-31 | 2021-01-22 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112646163A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of cardanol polyether polyol with high pentane intersolubility |
| CN113527618A (en) * | 2021-08-06 | 2021-10-22 | 南京金栖化工集团有限公司 | Preparation method and application of flame-retardant flatulence slow-rebound combined polyether polyol |
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2019
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250858A (en) * | 2020-08-31 | 2021-01-22 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112250858B (en) * | 2020-08-31 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol |
| CN112646163A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of cardanol polyether polyol with high pentane intersolubility |
| CN113527618A (en) * | 2021-08-06 | 2021-10-22 | 南京金栖化工集团有限公司 | Preparation method and application of flame-retardant flatulence slow-rebound combined polyether polyol |
| CN113527618B (en) * | 2021-08-06 | 2022-11-01 | 南京金栖化工集团有限公司 | Preparation method and application of flame-retardant flatulence slow-rebound combined polyether polyol |
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Application publication date: 20200331 |