CN111777734A - Flame-retardant polyether material for polyurethane foaming product - Google Patents
Flame-retardant polyether material for polyurethane foaming product Download PDFInfo
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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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- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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- 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
- C08G65/2603—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 oxygen
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- 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
- C08G65/2603—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 oxygen
- C08G65/2606—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 oxygen containing hydroxyl groups
- C08G65/2609—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 oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention discloses a flame-retardant polyether material for polyurethane foam products, which uses a mixed material of cresol phosphate-based polyether polyol and melamine-based polyether polyol as a material substrate of a flame retardant, wherein the cresol phosphate-based polyether polyol contains a benzene ring structure, so that the mechanical property of the polyurethane foam product can be effectively improved, the contents of a molecular hard section and a molecular soft section are increased, the closed-cell rate of the polyurethane foam product is improved, a melamine derivative in the melamine-based polyether polyol has good thermal stability, the fire resistance of the polyurethane foam product is improved, two alcohol substrate materials are mixed by adopting aluminum hydroxide, the flame-retardant property of the surface of the polyurethane foam product material is improved, aluminum hydroxide forms a film-shaped structure on the surface of the material, the interior of the polyurethane foam product material can be insulated while flame-retardant, and the heat conductivity coefficient and the water absorption rate of the polyurethane foam product material are reduced, is more suitable for product heat preservation.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a flame-retardant polyether material for a polyurethane foaming product.
Background
The polyurethane rigid foam is a high molecular polymer which is prepared by mixing isocyanate and polyether serving as main raw materials through a special device under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like and spraying the mixture at high pressure to foam on site, is suitable for sofa furniture, pillows, cushions, toys, clothes, sound insulation linings and the like, is sometimes suitable for the fields of pipe-channel heat insulation, building heat insulation, cold storage heat insulation and the like due to low heat conductivity coefficient and good waterproof performance, most of the conventional flame-retardant polyether materials for polyurethane foam products adopt polyether polyol formed by white polyether or glycerol and epoxide, although the materials have good water resistance and impact resistance, the polyether polyol formed by the glycerol and the epoxide contains a large amount of active hydrogen, and is not beneficial to reducing the closed-cell rate of the polyurethane foam products in the using process, thereby reducing the production quality of the polyurethane foam products, the polyurethane foam product has poor thermal insulation performance.
Disclosure of Invention
The invention aims to provide a flame-retardant polyether material for a polyurethane foaming product, which can improve the closed cell rate of the polyurethane foaming product, preserve the heat of the interior of the polyurethane foaming product material while resisting flame, reduce the heat conductivity coefficient and the water absorption of the polyurethane foaming product material, and is more suitable for product heat preservation, so as to solve the problems that polyether polyol formed by glycerol and epoxide, which is proposed in the background technology, contains a large amount of active hydrogen, and is not beneficial to reducing the closed cell rate of the polyurethane foaming product in the using process, so that the production quality of the polyurethane foaming product is reduced, and the heat preservation performance of the polyurethane foaming product is poor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20-35 parts of phosphoric acid cresol fat-based polyol, 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin, 0-10 parts of catalyst, 0-10 parts of propylene oxide and 10-20 parts of aluminum hydroxide.
Preferably, the cresyl phosphate polyol is obtained by mixing trityl phosphate and diethanol amine and then carrying out vacuum distillation in a 37% formaldehyde aqueous solution environment, wherein the moisture content in the cresyl phosphate polyol is less than 0.05%.
Preferably, the cresol phosphate based polyol, the methanol and the formaldehyde are used as initiators, and the cresol phosphate based polyol, the methanol and the formaldehyde are added with the polyolefin and the catalyst to react to obtain the cresol phosphate based polyether polyol.
Preferably, the viscosity of the cresol phosphate ester-based polyol at 25 ℃ is 2000-3500 MPa.s, the hydroxyl value content (KOH) of the cresol phosphate ester-based polyol is 20-35mg/g, the pH value of the cresol phosphate ester-based polyol is 7.0-8.5, the acid value is 0.10-0.16, and the solid content is 30.7%.
Preferably, the feeding ratio of the cresol phosphate-based polyether polyol to the polyolefin in the reaction is 1: 0.5.
Preferably, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA.
Preferably, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
The invention also provides a preparation method of the flame-retardant polyether material for the polyurethane foaming product, which comprises the following steps:
s1, adding trityl phosphate and diethanol amine into a reaction container, stirring uniformly under the protection of nitrogen, heating, adding 37% of formaldehyde aqueous solution, refluxing for 3 hours, and then carrying out reduced pressure distillation to obtain the cresol phosphate ester-based polyol with the moisture of less than 1%;
s2, adding 20-35 parts of cresol phosphate ester-based polyol, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, and heating the reaction kettle to 120 ℃ for reaction for 3 hours;
s3, reducing the pressure of the reaction kettle, introducing 0.1MPa nitrogen when the pressure in the reaction kettle is reduced to 0MPa, cooling to 100 ℃, preserving the temperature for 2 hours, and dehydrating and catalyzing to obtain the cresol phosphate-based polyether polyol;
s4, adding 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, uniformly stirring in a nitrogen environment, and heating the reaction kettle to 150 ℃ for reaction for 5 hours;
s5, reducing the pressure of the reaction kettle, and removing water and the catalyst in the reaction kettle to obtain melamine polyether polyol when the pressure in the reaction kettle is reduced to 0 MPa;
s6, adding the cresol phosphate-based polyether polyol and the melamine-based polyether polyol into a reaction kettle, uniformly stirring in a nitrogen environment, heating to 150 ℃, then adding 10-20 parts of aluminum hydroxide and 0-10 parts of catalyst, uniformly stirring, then reducing the pressure of the reaction kettle, and when the pressure in the reaction kettle is reduced to 0MPa, removing the water and the catalyst in the reaction kettle to obtain the finished flame-retardant polyether material.
Preferably, the addition ratio of the cresol phosphate-based polyether polyol to the melamine-based polyether polyol to the aluminum hydroxide is 1:1: 0.5-1.5.
The invention provides a flame-retardant polyether material for polyurethane foam products, which uses a mixed material of cresol phosphate-based polyether polyol and melamine-based polyether polyol as a material substrate of a flame retardant, wherein the cresol phosphate-based polyether polyol contains a benzene ring structure, so that the mechanical property of the polyurethane foam product can be effectively improved, the contents of a molecular hard section and a molecular soft section are increased, the closed-cell rate of the polyurethane foam product is improved, a melamine derivative in the melamine-based polyether polyol has good thermal stability, the fire resistance of the polyurethane foam product is improved, two alcohol substrate materials are mixed by adopting aluminum hydroxide, the flame-retardant property of the surface of the polyurethane foam product material is improved, the aluminum hydroxide forms a film-shaped structure on the surface of the material, the interior of the polyurethane foam product material can be insulated while flame-retardant, and the heat conductivity coefficient and the water absorption rate of the polyurethane foam product material are reduced, is more suitable for product heat preservation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20 parts of phosphate cresol base polyol, 20 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of catalyst and 20 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment with the concentration of 37%, the moisture content in the phosphate cresol base polyol is less than 0.05%, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, the polyolefin and the catalyst are added to react to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the temperature of 25 ℃ is 3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7%, the filling ratio of the phosphate cresol base polyether polyol to the polyolefin during the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
Example 2
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20 parts of phosphate cresol base polyol, 20 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of propylene oxide and 20 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment with the concentration of 37%, the moisture content in the phosphate cresol base polyol is less than 0.05%, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, the polyolefin and the catalyst are added for reaction to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the temperature of 25 ℃ is 3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7%, the introduction ratio of the phosphate cresol base polyether polyol to the polyolefin during the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
Example 3
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 30 parts of phosphate cresol base polyol, 20 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of catalyst and 10 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment with the concentration of 37%, the moisture content in the phosphate cresol base polyol is less than 0.05%, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, the polyolefin and the catalyst are added to react to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the temperature of 25 ℃ is 3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7%, the filling ratio of the phosphate cresol base polyether polyol to the polyolefin during the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
Example 4
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 30 parts of phosphate cresol base polyol, 20 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of propylene oxide and 10 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment of 37 percent, the moisture content in the phosphate cresol base polyol is less than 0.05 percent, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, polyolefin and a catalyst are added for reaction to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the environment of 25 ℃ is 2000-3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7 percent, the introduction ratio of the phosphate cresol base polyether polyol to the polyolefin in the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
Example 5
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20 parts of acid cresol base polyol, 30 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of catalyst and 10 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment with the concentration of 37%, the moisture content in the phosphate cresol base polyol is less than 0.05%, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, the polyolefin and the catalyst are added to react to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the temperature of 25 ℃ is 3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7%, the filling ratio of the phosphate cresol base polyether polyol to the polyolefin during the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
Example 6
The flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20 parts of phosphate cresol base polyol, 30 parts of melamine, 20 parts of formaldehyde, 5 parts of methanol, 10 parts of polyolefin, 5 parts of propylene oxide and 10 parts of aluminum hydroxide, wherein the phosphate cresol base polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde aqueous solution environment with the concentration of 37%, the moisture content in the phosphate cresol base polyol is less than 0.05%, the phosphate cresol base polyol, the methanol and the formaldehyde are used as initiators, polyolefin and a catalyst are added for reaction to obtain the phosphate cresol base polyether polyol, the viscosity of the phosphate cresol base polyol at the temperature of 25 ℃ is 3500 MPa.s, the hydroxyl value content (KOH) of the phosphate cresol base polyol is 20-35mg/g, the pH value of the phosphate cresol base polyol is 7.0-8.5, the acid value is 0.10-0.16, the solid content is 30.7%, the introduction ratio of the phosphate cresol base polyether polyol to the polyolefin during the reaction is 1:0.5, the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA, the cresol phosphate ester-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
The invention also provides a preparation method of the flame-retardant polyether material for the polyurethane foaming product, which comprises the following steps:
s1, adding trityl phosphate and diethanol amine into a reaction container, stirring uniformly under the protection of nitrogen, heating, adding 37% of formaldehyde aqueous solution, refluxing for 3 hours, and then carrying out reduced pressure distillation to obtain the cresol phosphate ester-based polyol with the moisture of less than 1%;
s2, adding 20-35 parts of cresol phosphate ester-based polyol, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, and heating the reaction kettle to 120 ℃ for reaction for 3 hours;
s3, reducing the pressure of the reaction kettle, introducing 0.1MPa nitrogen when the pressure in the reaction kettle is reduced to 0MPa, cooling to 100 ℃, preserving the temperature for 2 hours, and dehydrating and catalyzing to obtain the cresol phosphate-based polyether polyol;
s4, adding 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, uniformly stirring in a nitrogen environment, and heating the reaction kettle to 150 ℃ for reaction for 5 hours;
s5, reducing the pressure of the reaction kettle, and removing water and the catalyst in the reaction kettle to obtain melamine polyether polyol when the pressure in the reaction kettle is reduced to 0 MPa;
s6, adding the cresol phosphate-based polyether polyol and the melamine-based polyether polyol into a reaction kettle, uniformly stirring in a nitrogen environment, heating to 150 ℃, then adding 10-20 parts of aluminum hydroxide and 0-10 parts of catalyst, uniformly stirring, then reducing the pressure of the reaction kettle, removing the water and the catalyst in the reaction kettle when the pressure in the reaction kettle is reduced to 0MPa, and obtaining a finished flame-retardant polyether material, wherein the adding amount ratio of the cresol phosphate-based polyether polyol to the melamine-based polyether polyol to the aluminum hydroxide is 1:1: 0.5-1.5.
In summary, the following steps: the flame-retardant polyether material for the polyurethane foaming product uses a mixed material of cresol phosphate-based polyether polyol and melamine-based polyether polyol as a material substrate of a flame retardant, a benzene ring structure contained in the cresol phosphate-based polyether polyol can effectively improve the mechanical property of the polyurethane foaming product, the contents of a molecular hard section and a molecular soft section are both high, the closed cell rate of the polyurethane foaming product is improved, a melamine derivative in the melamine-based polyether polyol has good thermal stability, the fire resistance of the polyurethane foaming product is improved, two alcohol substrate materials are mixed by adopting aluminum hydroxide, the flame retardant property of the surface of the polyurethane foaming product material is improved, aluminum hydroxide forms a film-shaped structure on the surface of the material, the interior of the polyurethane foaming product material can be insulated while flame retardance is realized, and the heat conductivity coefficient and the water absorption rate of the polyurethane foaming product material are reduced, is more suitable for product heat preservation.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The flame-retardant polyether material for the polyurethane foaming product is characterized in that: the flame-retardant polyether material for the polyurethane foaming product comprises the following components in parts by weight: 20-35 parts of phosphoric acid cresol fat-based polyol, 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin, 0-10 parts of catalyst, 0-10 parts of propylene oxide and 10-20 parts of aluminum hydroxide.
2. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol is obtained by mixing triphenylmethyl phosphate and diethanol amine and then carrying out reduced pressure distillation in a formaldehyde water solution environment with the concentration of over 37 percent, and the moisture content in the phosphoric acid cresol fat-based polyol is less than 0.05 percent.
3. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol, the methanol and the formaldehyde are used as initiators, and the phosphoric acid cresol fat-based polyether polyol is obtained by adding polyolefin and a catalyst and reacting.
4. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the viscosity of the cresol phosphate ester-based polyol at 25 ℃ is 2000-3500 MPa.s, the hydroxyl value content (KOH) of the cresol phosphate ester-based polyol is 20-35mg/g, the pH value of the cresol phosphate ester-based polyol is 7.0-8.5, the acid value is 0.10-0.16, and the solid content is 30.7%.
5. The flame-retardant polyether material for polyurethane foam products as claimed in claim 3, wherein: the charging ratio of the cresol phosphate-based polyether polyol to the polyolefin during the reaction is 1: 0.5.
6. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the catalyst can be one of N, N-dimethylcyclohexylamine, triethylamine, diethanolamine and DMEA.
7. The flame-retardant polyether material for polyurethane foam products as claimed in claim 1, wherein: the phosphoric acid cresol fat-based polyol, the melamine and the formaldehyde are used as initiators, and the melamine-based polyether polyol is obtained by adding the polyolefin and the catalyst and then reacting.
8. A method for preparing the flame-retardant polyether material for polyurethane foam products as claimed in claim 1, which is characterized in that: the method comprises the following steps:
s1, adding trityl phosphate and diethanol amine into a reaction container, stirring uniformly under the protection of nitrogen, heating, adding 37% of formaldehyde aqueous solution, refluxing for 3 hours, and then carrying out reduced pressure distillation to obtain the cresol phosphate ester-based polyol with the moisture of less than 1%;
s2, adding 20-35 parts of cresol phosphate ester-based polyol, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, and heating the reaction kettle to 120 ℃ for reaction for 3 hours;
s3, reducing the pressure of the reaction kettle, introducing 0.1MPa nitrogen when the pressure in the reaction kettle is reduced to 0MPa, cooling to 100 ℃, preserving the temperature for 2 hours, and dehydrating and catalyzing to obtain the cresol phosphate-based polyether polyol;
s4, adding 20-35 parts of melamine, 20-35 parts of formaldehyde, 2-8 parts of methanol, 10-15 parts of polyolefin and 0-10 parts of catalyst or 0-10 parts of propylene oxide into a reaction kettle, uniformly stirring in a nitrogen environment, and heating the reaction kettle to 150 ℃ for reaction for 5 hours;
s5, reducing the pressure of the reaction kettle, and removing water and the catalyst in the reaction kettle to obtain melamine polyether polyol when the pressure in the reaction kettle is reduced to 0 MPa;
s6, adding the cresol phosphate-based polyether polyol and the melamine-based polyether polyol into a reaction kettle, uniformly stirring in a nitrogen environment, heating to 150 ℃, then adding 10-20 parts of aluminum hydroxide and 0-10 parts of catalyst, uniformly stirring, then reducing the pressure of the reaction kettle, and when the pressure in the reaction kettle is reduced to 0MPa, removing the water and the catalyst in the reaction kettle to obtain the finished flame-retardant polyether material.
9. The method for preparing the flame-retardant polyether material for the polyurethane foam product according to claim 8, wherein the method comprises the following steps: the addition ratio of the cresol phosphate fat-based polyether polyol to the melamine polyether polyol to the aluminum hydroxide is 1:1: 0.5-1.5.
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