CN113980264B - Preparation method and application of flame-retardant polyether polyol - Google Patents
Preparation method and application of flame-retardant polyether polyol Download PDFInfo
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- 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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- 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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- 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
- C08G65/2642—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 catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- 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
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention provides a preparation method and application of flame-retardant polyether polyol, and belongs to the field of organic synthesis. The preparation method comprises the following steps: adding a mixture of phosphite ester, carbon tetrachloride and anhydrous tetrahydrofuran in a nitrogen atmosphere at 0-5 ℃, dropwise adding a mixture of N-allylmethylamine, triethylamine and anhydrous tetrahydrofuran, and reacting at 15-30 ℃ for 6-12h to obtain allylmethyl phosphoramidate; adding allyl methyl phosphoramidate at 35-45 ℃, adding formic acid, dropwise adding hydrogen peroxide at 45-55 ℃, and continuing to react at 45-55 ℃ for 4-6 h; and (3) carrying out coordination polymerization reaction on low molecular weight polyol, 1-methyl phosphoramidate-2,3-propylene oxide and propylene oxide at 145-155 ℃ to obtain the flame-retardant polyether polyol. The flame-retardant polyether polyol can be used for preparing polyurethane adhesives and polyurethane foams with good flame retardance.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method and application of flame-retardant polyether polyol.
Background
The polyurethane material has the characteristics of strong wear resistance, excellent shock absorption performance, excellent machining performance and the like, and polyurethane products with various performances can be prepared by selecting main raw materials and optimally designing a formula. Due to excellent performance, the polyurethane material is widely applied to the fields of clothes, shoes and hats, building outer walls, pipelines, aerospace, furniture, automobiles, medical treatment and the like, but the flame retardant property of the existing polyurethane material is not satisfactory.
Disclosure of Invention
The invention aims to provide a preparation method of flame-retardant polyether polyol, and the obtained flame-retardant polyether polyol can be used for preparing polyurethane adhesives and polyurethane foams with good flame retardance.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of flame-retardant polyether polyol comprises the following steps:
(1) Adding a mixture of phosphite ester, carbon tetrachloride and anhydrous tetrahydrofuran into a reaction kettle in a nitrogen atmosphere at 0-5 ℃, dropwise adding a mixture of N-allylmethylamine, triethylamine and anhydrous tetrahydrofuran after stirring, raising the temperature to 15-30 ℃ after dropwise adding, and reacting for 6-12h under a stirring state to obtain allylmethylamino phosphate;
(2) Adding allyl methyl phosphoramidate into a reaction kettle at 35-45 ℃, adding formic acid, dropwise adding hydrogen peroxide at 45-55 ℃, and continuously reacting for 4-6h at 45-55 ℃ under a stirring state after dropwise adding to obtain 1-methyl phosphoramidate-2,3-epoxypropane;
(3) The low molecular weight polyol, 1-methyl phosphoramidate-2,3-propylene oxide and propylene oxide are subjected to coordination polymerization reaction at 145-155 ℃ under the catalysis of a catalyst to obtain the flame-retardant polyether polyol.
In the invention, the phosphite ester in the step (1) is one or more of dimethyl phosphite, diethyl phosphite and diphenyl phosphite.
In the present invention, the molar ratio of the phosphite to the N-allylmethylamine in step (1) is 1:1-1.5; the molar ratio of the phosphite ester to the carbon tetrachloride to the triethylamine is 1:1-1.5. The molar ratio of the phosphite ester to the total anhydrous tetrahydrofuran in the step (1) is 1:8-12, and the molar ratio of tetrahydrofuran used in the front part and the rear part is 1.4-0.8.
In the invention, the molar ratio of the allyl methyl phosphoramidate, the formic acid and the hydrogen peroxide in the step (2) is 1.
In the present invention, the low-molecular polyol in the step (3) has a functionality of 2 to 3 and a number average molecular weight of 200 to 1000; the catalyst is a double metal cyanide complex catalyst.
In the invention, the mass ratio of the double metal cyanide complex catalyst to the flame-retardant polyether polyol in the step (3) is 1.
The invention also provides application of the prepared flame-retardant polyether polyol in preparation of a polyurethane material.
The preparation method comprises the following reaction processes:
Atherton-Todd reaction:
in-situ epoxidation reaction:
coordination polymerization reaction:
according to the invention, anhydrous tetrahydrofuran is used as an organic solvent, triethylamine is used as a catalyst, and carbon tetrachloride, phosphite ester and N-allylmethylamine are subjected to Atherton-Todd reaction to generate allylmethyl phosphoramidate; then, in-situ epoxidation is carried out on the allyl methyl phosphoramidate under the action of formic acid and hydrogen peroxide to generate 1-dimethyl methyl phosphoramidate-2,3-propylene oxide; finally, the low molecular weight polyol, 1-methyl phosphoramidate-2,3-propylene oxide and propylene oxide are subjected to coordination polymerization reaction at 145-155 ℃ under the catalysis of a double metal cyanide complex catalyst to obtain the flame-retardant polyether polyol.
The invention has the beneficial effects that:
1. the phosphamide [ P (O) -N ] structure is introduced to the molecular side chain of polyether polyol through Atherton-Todd reaction, in-situ epoxidation reaction and coordination polymerization reaction, and the flame-retardant polyether polyol with high flame-retardant element content can be prepared.
2. Compared with an additive flame retardant, the flame retardant has the advantages of no compatibility problem, reduced system viscosity, good migration resistance and no influence on the original physical and mechanical properties of the material.
3. The flame-retardant polyether polyol prepared by the invention does not contain halogen, and the P (O) -N structure provides excellent heat resistance and excellent flame retardance under the synergistic action of nitrogen and phosphorus.
4. The polyurethane material prepared from the flame-retardant polyether polyol has an oxygen index of more than 28, has a good flame-retardant effect, is excellent in high-temperature resistance, good in smoke suppression effect during flame retardance, free of toxic gas release, safe and environment-friendly, and meets the ever-stricter flame-retardant requirement.
5. The flame-retardant polyether polyol can be used for preparing polyurethane adhesives and polyurethane foams with good flame retardance.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Example 1
Preparation of dimethyl allylmethylaminophosphate by Atherton-Todd reaction as follows: adding a mixture of 1mol of dimethyl phosphite, 1.1mol of carbon tetrachloride and 6mol of anhydrous tetrahydrofuran into a reaction kettle at 5 ℃ in a nitrogen atmosphere, starting stirring, dropwise adding a mixture of 1.05mol of N-allylmethylamine, 1.1mol of triethylamine and 3mol of anhydrous tetrahydrofuran, and finishing dropwise adding within 2 hours; then raising the temperature to 25 ℃, and reacting for 10 hours at the temperature of 25 ℃ under a stirring state; finally, the allyl methyl amino dimethyl phosphate is obtained after filtration and reduced pressure distillation.
1-dimethyl methylaminophosphate-2,3-propylene oxide was prepared by in situ epoxidation according to the following procedure: at 40 ℃, adding 0.9mol of allyl methyl dimethyl phosphoramidate into a reaction kettle, adding 0.8mol of formic acid, heating to 50 ℃, dropwise adding 0.9mol of hydrogen peroxide (provided in the form of 30% hydrogen peroxide aqueous solution by mass percentage concentration) at 50 ℃, after 1h of dropwise adding, continuously reacting for 6h at 50 ℃ under a stirring state; finally, discharging after water washing and reduced pressure distillation to obtain the 1-methyl amino dimethyl phosphate-2,3-epoxypropane.
The flame-retardant polyether polyol A is prepared by coordination polymerization according to the following method: adding 100g of polyether polyol N-204 (propylene glycol polyoxypropylene ether, molecular weight 400, purchased from Jiangsu clock chemical Co., ltd.) and 100ppm of double metal cyanide complex catalyst (DMC catalyst, purchased from Huayin Mitsui chemical Co., ltd.), starting stirring, replacing with nitrogen for 3 times, vacuumizing to-0.1 MPa, and heating to 150 ℃ while vacuumizing; keeping the temperature at 150 ℃ for 1h under the condition that the vacuum degree is-0.1 MPa, then closing a vacuum valve and stopping heating, introducing 30g of a mixture of propylene oxide and 1-dimethyl methylaminophosphate-2,3-propylene oxide (the mass ratio of the propylene oxide to the 1-dimethyl methylaminophosphate-2,3-propylene oxide is 5:3), after the pressure is reduced and the temperature is increased, continuously introducing 370g of a mixture of the propylene oxide and the 1-dimethyl methylaminophosphate-2,3-propylene oxide (the mass ratio of the propylene oxide to the 1-dimethyl methylaminophosphate-2,3-propylene oxide is 5:3), and controlling the pressure to be 0.1MPa and the temperature to be 145 ℃ in the continuous introducing process; after the alkylene oxide feeding is finished, preserving heat for 1h at 145 ℃, and then vacuumizing for 1h; finally, cooling to room temperature to obtain the flame-retardant polyether polyol A. It is particularly pointed out that the amount of DMC catalyst used per kg of reactants (polyether polyol N-204, propylene oxide and dimethyl-1-methylaminophosphate-2,3-propylene oxide) is 100mg.
Example 2
1-Methylaminophosphoric acid dimethyl ester-2,3-propylene oxide was prepared as in example 1.
The flame retardant polyether polyol B is prepared by coordination polymerization according to the following method: adding 100g of polyether polyol N-306 (glycerol polyoxypropylene ether, molecular weight 600, purchased from Kyoho Bell chemical Co., ltd.) and 100ppm of DMC catalyst into a reaction kettle, starting stirring, performing nitrogen replacement for 3 times, vacuumizing to the vacuum degree of-0.1 MPa, and heating to 150 ℃ while vacuumizing; under the condition that the vacuum degree is-0.1 MPa, after heat preservation is carried out for 1h at 150 ℃, a vacuum valve is closed, heating is stopped, a mixture of 30g of propylene oxide and 1-dimethyl methylaminophosphate-2,3-propylene oxide is introduced (the mass ratio of the propylene oxide to the 1-dimethyl methylaminophosphate-2,3-propylene oxide is 5:3), after the pressure is reduced and the temperature is increased, a mixture of 370g of propylene oxide and 1-dimethyl methylaminophosphate-2,3-propylene oxide is continuously introduced (the mass ratio of the propylene oxide to the 1-dimethyl methylaminophosphate-2,3-propylene oxide is 5:3), the pressure is controlled to be 0.1MPa in the continuous introducing process, and the temperature is controlled to be 145 ℃; after the alkylene oxide feeding is finished, preserving the heat for 1h at 145 ℃, and then vacuumizing for 1h; finally, cooling to room temperature to obtain the flame-retardant polyether polyol B for later use. It is particularly pointed out that the DMC catalyst is used in an amount of 100mg per kg of reactants (polyether polyol N-306, propylene oxide and dimethyl-1-methylaminophosphate-2,3-propylene oxide).
Comparative example 1
A common polyether polyol ZSN-220 (propylene glycol polyoxypropylene ether, molecular weight 2000, available from Jiangsu Bosch chemical Co., ltd.).
Comparative example 2
A common polyether polyol ZSN-330 (glycerol polyoxypropylene ether, molecular weight 3000, available from Jiangsu Boehringer Mannheim chemical Co., ltd.).
Comparative example 3
100 parts by mass of ordinary polyether polyol ZSN-220 (same as above) and 30 parts by mass of dimethyl allylmethylaminophosphate are mixed to obtain flame retardant polyether polyol C.
Comparative example 4
100 parts by mass of ordinary polyether polyol ZSN-330 (same as above) and 30 parts by mass of dimethyl allylmethylaminophosphate are mixed to obtain flame-retardant polyether polyol D.
Comparative example 5
Dimethyl bis (2-hydroxyethyl) phosphoramidate was prepared by the Atherton-Todd reaction as follows: adding a mixture of 1mol of dimethyl phosphite, 1.1mol of carbon tetrachloride and 6mol of anhydrous tetrahydrofuran into a reaction kettle at 5 ℃ in a nitrogen atmosphere, starting stirring, dropwise adding a mixture of 1.05mol of diethanolamine, 1.1mol of triethylamine and 3mol of anhydrous tetrahydrofuran, and finishing dropwise adding for 2 h; then raising the temperature to 25 ℃, and reacting for 10 hours at the temperature of 25 ℃ under a stirring state; finally, the mixture is filtered, decompressed and distilled and discharged to obtain the bis (2-hydroxyethyl) amino dimethyl phosphate.
Adding 100g of bis (2-hydroxyethyl) dimethyl phosphoramidate and 2.3g of catalyst KOH into a reaction kettle, starting stirring, performing nitrogen replacement for 3 times, vacuumizing to the vacuum degree of-0.1 MPa, and heating to 120 ℃ while vacuumizing; keeping the temperature of 120 ℃ for 1h under the vacuum degree of-0.1 MPa, closing a vacuum valve, stopping heating, introducing 30g of propylene oxide, continuously introducing 773g of propylene oxide after the pressure is reduced and the temperature is increased, and controlling the pressure to be 0.3MPa and the temperature to be 120 ℃ in the continuous introducing process; after the feeding of the alkylene oxide is finished, preserving heat for 1h at 120 ℃, and then vacuumizing for 1h; adding 11.5g refining agent CP-2 (purchased from Dallas Special adsorbent Co., ltd.), stirring for 1h, vacuumizing for 1h, and maintaining the temperature at 120 deg.C; and finally, filtering and cooling to room temperature to obtain the flame-retardant polyether polyol E for later use.
Comparative example 6
N, N', N "-tris (2-hydroxyethylmethyl) phosphotriamide was prepared by the Atherton-Todd reaction as follows: adding a mixture of 1mol of phosphorus oxychloride and 6mol of anhydrous tetrahydrofuran into a reaction kettle in a nitrogen atmosphere at 5 ℃, dropwise adding a mixture of 3.15mol of 2- (methylamino) ethanol, 3.3mol of triethylamine and 3mol of anhydrous tetrahydrofuran after starting stirring, heating to 25 ℃ after completing dropwise adding for 3h, and reacting for 10h at 25 ℃ under a stirring state; filtering, distilling under reduced pressure, and discharging to obtain N, N' -tris (2-hydroxyethyl methyl) phosphoric triamide.
Adding 100gN, N' -tris (2-hydroxyethyl methyl) phosphoric triamide and 3.1g of catalyst KOH into a reaction kettle, starting stirring, performing nitrogen replacement for 3 times, vacuumizing to the vacuum degree of-0.1 MPa, and heating to 120 ℃ while vacuumizing; keeping the temperature of 120 ℃ for 1h under the vacuum degree of-0.1 MPa, closing a vacuum valve, stopping heating, introducing 30g of propylene oxide, continuously introducing 1087g of propylene oxide after the pressure is reduced and the temperature is increased, and keeping the pressure at 0.3MPa and the temperature at 120 ℃ in the continuous introducing process; after the alkylene oxide feeding is finished, preserving heat for 1h at 120 ℃, and then vacuumizing for 1h; adding 15.5g refining agent CP-2 (purchased from Dallas Special adsorbent Co., ltd.), stirring at 120 deg.C for 1 hr, and vacuumizing for 1 hr; and finally, filtering and cooling to room temperature to obtain the flame-retardant polyether polyol F for later use.
The results of the tests for the polyether polyol obtained in each of the examples and comparative examples are shown in Table 1.
TABLE 1 polyether polyol index test results
As can be seen from Table 1, the flame-retardant polyether polyol prepared by the method disclosed by the invention has the advantages that the viscosity is higher than that of the common polyether polyol, other indexes are close, and the viscosity is also at a lower level, so that the method disclosed by the invention is reasonable, the qualified flame-retardant polyether polyol product can be prepared, and the flame-retardant polyether polyol has the characteristics of low viscosity and low chromaticity. Wherein, the flame-retardant polyether polyols E and F are obtained by taking micromolecules containing a phosphorus amide structure as an initiator and grafting PO.
The polyurethane adhesive is prepared from flame-retardant polyether polyol A, common polyether polyol ZSN-220, flame-retardant polyether polyol C and flame-retardant polyether polyol E respectively, and the formula of the polyurethane adhesive is as follows: the component A comprises: 40 parts (by mass, the same below) of polyether polyol, 30 parts of acrylic resin BR-113 (purchased from Mitsubishi chemical), and 30 parts of polyester polyol Dynacoll7320 (purchased from Yingchu Special chemical); and B component: 47 parts of diphenylmethane diisocyanate MDI-100 (from Vanda chemical).
Vacuumizing the component A at 120 ℃ for 1h, cooling to 80 ℃, adding the component B in batches to control the temperature to be 80-90 ℃, stirring while vacuumizing after adding, heating to 120 ℃, reacting at 120 ℃ for 0.5h, cooling, discharging, sealing and storing for later use.
The polyurethane Adhesive prepared from the flame-retardant polyether polyol A, the common polyether polyol ZSN-220, the flame-retardant polyether polyol C and the flame-retardant polyether polyol E is numbered as Adhesive1, adhesive2, adhesive3 and Adhesive4 in sequence.
The performance test of each polyurethane adhesive is shown in table 2.
TABLE 2 comparison of the Properties of the polyurethane Adhesives
As can be seen from Table 2, the melt viscosity of the polyurethane adhesive is improved but not greatly improved by adopting the flame-retardant polyether polyol A to replace ZSN-220; the bonding strength is equivalent; the use of the flame-retardant polyether polyol A is proved not to influence the original physical and mechanical properties of the adhesive. In addition, the oxygen index is 30 and more than 28, and the flame-retardant polyether polyol A cannot be combusted, which indicates that the flame-retardant polyether polyol A can enable the polyurethane adhesive to have good flame retardance. The flame-retardant polyether polyol C is a mixture of ZSN-220 and micromolecule additive phosphoramide, belongs to additive flame-retardant polyether polyol, and has the advantages of low compatibility of the micromolecule additive phosphoramide and polyurethane, reduced original physical and mechanical properties of the adhesive, high melt viscosity, oxygen index smaller than 28 and flammability. Although the use of the flame-retardant polyether polyol E does not affect the original physical and mechanical properties of the adhesive, the flame-retardant polyether polyol E has an oxygen index of not more than 28 and can still be burnt, so that the flame retardance is limited.
Respectively adopting flame-retardant polyether polyol B, common polyether polyol ZSN-330, flame-retardant polyether polyol D and flame-retardant polyether polyol F to prepare polyurethane foam, wherein the formula of the polyurethane foam is as follows: the component A comprises: 30 parts (by mass, the same applies hereinafter) of polyether polyol, 70 parts of polyether polymer polyol GP2045 (purchased from Jiangsu Mount Conn.), 1.5 parts of silicone oil L-580 (purchased from Mitigo high-new material), 4 parts of water, 0.3 part of catalyst triethylene diamine A33 (purchased from Mitigo high-new material) and 0.3 part of catalyst stannous octoate. The component B comprises: 48.5 parts of toluene diisocyanate TDI-80 (from Cangzhou Daizhig). And uniformly mixing the component A and the component B, pouring the mixture into a mold, curing and drying to obtain the polyurethane foam material.
The numbers of polyurethane foams corresponding to the flame-retardant polyether polyol B, the common polyether polyol ZSN-330, the flame-retardant polyether polyol D and the flame-retardant polyether polyol F are respectively Foam1, foam2, foam3 and Foam4.
The performance test of each polyurethane foam is shown in table 3.
TABLE 3 comparison of Foam1 and Foam2 Performance
As can be seen from Table 3, the flame-retardant polyether polyol B is used for replacing ZSN-330, so that the mechanical properties of the polyurethane foam are close to each other, and the oxygen index is greatly improved, which indicates that the use of the flame-retardant polyether polyol B does not affect the original mechanical properties of the product and can also enable the product to have flame retardance. The flame-retardant polyether polyol D contains micromolecular additive phosphoramide, has poor compatibility with polyurethane foam, reduces mechanical property and has limited improvement of oxygen index. Although the flame retardant polyether polyol F did not affect the original mechanical properties of the foam, the oxygen index did not exceed 28 and the flame retardancy was limited.
On the premise of not influencing the original physical and mechanical properties of the polyurethane material and enabling the oxygen index of the polyurethane material to be larger than 28, the preparation of the reactive flame-retardant polyether polyol with low viscosity, low chroma and high flame-retardant element content has great difficulty.
In conclusion, the preparation process of the flame-retardant polyether polyol with the phosphoramide [ P (O) -N ] structure and the high flame-retardant element content on the molecular side chain is reasonable, and all indexes of the flame-retardant polyether polyol are excellent. When the polyurethane modified epoxy resin is applied to polyurethane products, the compatibility problem does not exist, the migration resistance is good, the original mechanical property of the polyurethane products is not changed, the oxygen index of the polyurethane is high, and the polyurethane has excellent flame retardance.
Although the embodiments of the present invention have been described in detail, the present invention is not limited to the embodiments, and equivalent changes or modifications made within the scope of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and scope of the present invention.
Claims (6)
1. A preparation method of flame-retardant polyether polyol is characterized by comprising the following steps:
(1) Adding a mixture of phosphite ester, carbon tetrachloride and anhydrous tetrahydrofuran into a reaction kettle in a nitrogen atmosphere at 0-5 ℃, dropwise adding a mixture of N-allylmethylamine, triethylamine and anhydrous tetrahydrofuran after stirring, raising the temperature to 15-30 ℃ after dropwise adding, and reacting 6-12h under a stirring state to obtain allylmethyl phosphoramidate;
(2) Adding allyl methyl phosphoramidate into a reaction kettle at 35-45 ℃, adding formic acid, dropwise adding hydrogen peroxide at 45-55 ℃, and continuously reacting for 4-6h at 45-55 ℃ under a stirring state after dropwise adding is finished to obtain 1-methyl phosphoramidate-2,3-epoxypropane;
(3) Carrying out coordination polymerization reaction on low molecular weight polyol, 1-methyl phosphoramidate-2,3-propylene oxide and propylene oxide at 145-155 ℃ under the catalysis of a catalyst to obtain flame-retardant polyether polyol; the low molecular weight polyalcohol has the functionality of 2-3 and the number average molecular weight of 200-1000; the catalyst is a double metal cyanide complex catalyst.
2. The method of producing the flame retardant polyether polyol according to claim 1, wherein: and (2) the phosphite ester in the step (1) is one or more of dimethyl phosphite, diethyl phosphite and diphenyl phosphite.
3. The process according to claim 1 or 2, wherein the molar ratio of phosphite to N-allylmethylamine in step (1) is 1:1-1.5; the molar ratio of the phosphite ester to the carbon tetrachloride to the triethylamine is 1:1-1.5.
4. The process according to claim 3, wherein the molar ratio of allylmethylaminophosphate, formic acid and hydrogen peroxide in the step (2) is 1.
5. The method of preparing a flame retardant polyether polyol according to claim 4, characterized in that: the mass ratio of the double metal cyanide complex catalyst to the flame-retardant polyether polyol in the step (3) is 1.
6. Use of the flame-retardant polyether polyol prepared according to claim 1 for the preparation of polyurethane materials.
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| CN116199961B (en) * | 2023-02-09 | 2024-05-07 | 苏州辰灿电子有限公司 | High-temperature-resistant corrosion-resistant wire harness material and preparation method thereof |
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