CN110643030A - Preparation method of hard foam flame-retardant polyether polyol for all-water foaming - Google Patents

Preparation method of hard foam flame-retardant polyether polyol for all-water foaming Download PDF

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CN110643030A
CN110643030A CN201911001613.6A CN201911001613A CN110643030A CN 110643030 A CN110643030 A CN 110643030A CN 201911001613 A CN201911001613 A CN 201911001613A CN 110643030 A CN110643030 A CN 110643030A
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polyether polyol
water foaming
preparation
water
hard foam
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CN110643030B (en
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张宝银
吕兴连
张坤
魏学福
米新强
周小光
付文辉
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BEFAR GROUP CO LTD
Binhua Technology Co ltd
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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
    • C08G65/2612—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 aromatic or arylaliphatic hydroxyl groups
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G65/2603—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
    • 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
    • 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
    • C08G65/2642—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
    • C08G65/2648—Alkali metals or compounds thereof
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyethers (AREA)

Abstract

The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of hard foam flame-retardant polyether polyol for full water foaming, which takes cane sugar, low molecular weight polyol, halohydrin, phenolic resin and grease as initiators, takes alkali metal salt as a catalyst, and is introduced with a section of propylene oxide for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, and the crude ether is refined to obtain the finished product. The preparation method is simple in technological process operation, the obtained rigid foam flame-retardant polyether product for all-water foaming has low viscosity and good compatibility with water, and the polyurethane foam plastic product prepared by the preparation method has narrow density distribution, high strength, good dimensional stability and bonding strength, low heat conductivity coefficient and certain flame-retardant effect, and is particularly suitable for all-water foaming heat-insulating pipelines and other heat-insulating fields.

Description

Preparation method of hard foam flame-retardant polyether polyol for all-water foaming
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a preparation method of hard foam flame-retardant polyether polyol for full water foaming.
Background
In the prior art, various foaming agents are used for foaming hard polyether polyol, and at present, CFC systems are mostly used as the foaming agents, wherein HCFC-141B is mainly used, and some foaming agents even use national banned Freon-11 and the like, but the foaming agents are not environment-friendly and bring certain environmental hazards. In recent years, a plurality of units or individuals develop some all-water rigid polyether polyols, water is used for replacing a foaming agent, and the all-water foaming rigid foam polyether polyol technology is environment-friendly because carbon dioxide generated by the reaction of water and isocyanate is used as a foaming gas, ODP (ozone depletion potential) is zero, and GWP (greenhouse gas effect value) is 1, so that the all-water foaming rigid foam polyether polyol technology has a wide application prospect.
In the prior art, the synthesis process of the all-water foaming hard foam polyether polyol is mainly as follows: the catalyst is prepared by reacting sucrose, sorbitol, pentaerythritol, low molecular weight polyol or mixture thereof as initiator with propylene oxide by KOH catalysis or dimethylamine catalysis. However, the prior art rigid foam polyether polyol synthesis processes have the following disadvantages: (1) the all-water foaming hard foam polyether polyol product prepared by the process has high viscosity and high hydroxyl value, and in the all-water foaming polyether composite material, as no CFC, HCFC and other physical foaming agents which can be used as diluents exist, the viscosity of the compound composite material is high, and the mold filling property is poor when a foam product is processed; (2) when the hard foam polyether polyol in the prior art is subjected to full-water foaming, the speed of diffusing carbon dioxide in a foaming gas from a foam hole to the outside is 1.0 time faster than the speed of entering air into the foam hole, so that foam is induced to shrink and is easy to collapse; (3) when the rigid foam polyether polyol in the prior art is subjected to full-water foaming, as the using amount of water is larger, the rigid foam polyether polyol reacts with isocyanate to form more urea bonds, so that a foam body is brittle, and the bonding force with a heat insulation system is weak; (4) the hard polyether polyol for full water foaming in the prior art has the defect of poor flame retardant effect, and the flame retardant performance of the material is improved mainly by adding a non-reactive micromolecular flame retardant containing halogen, phosphorus and inorganic salts, however, the external addition type non-reactive flame retardant has the defects of poor storage stability in a combined material, influence on the strength of a product, easy migration out of the product and the like; (5) the rigid polyether polyol for full water foaming in the prior art has a complex preparation process and higher cost, so that the market share is very low, and the rigid polyether polyol meets great resistance in the actual popularization and application process.
Disclosure of Invention
The invention aims to provide a preparation method of rigid foam flame-retardant polyether polyol for full-water foaming, and the full-water foaming rigid foam polyether product obtained by the method has a hydroxyl value of 310-350 mgKOH, low viscosity and low cost; the foamed product has high compression strength and good dimensional stability; the adhesive force with a heat insulation system is strong; has certain flame retardant effect; the foam has low heat conductivity coefficient and good toughness.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of hard foam flame-retardant polyether polyol for full water foaming comprises the following steps:
(1) feeding and pretreating: adding sucrose, halohydrin, low-molecular-weight polyol, phenolic resin and grease into a reaction kettle, then adding an alkali metal salt catalyst, replacing for 3-5 times with nitrogen, then heating to 100-105 ℃, and performing vacuum dehydration until the water content of materials in the kettle is within 0.5% (wt);
(2) polymerization reaction: controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding propylene oxide to 80-90% of the total added mass of the propylene oxide, mixing the residual propylene oxide and ethylene oxide, dropwise adding the mixture of the propylene oxide and the ethylene oxide into a reaction kettle, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and then curing for 1.5-3.5 hours;
(3) and (3) post-treatment: and adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the product, namely the hard foam flame-retardant polyether polyol for full-water foaming.
Aiming at the defects of high polyether viscosity, high cost, unstable product quality, poor flame-retardant effect and the like existing in the current market application, a brand-new hard flame-retardant polyether polyol for full-water foaming is prepared by optimizing an initiator formula and simultaneously properly accessing EO (ethylene oxide), and the invention takes sucrose, halohydrin, low-molecular-weight polyol, a small amount of halohydrin, phenolic resin and grease as initiators and takes alkali metal salt as a catalyst and introduces a section of propylene oxide for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, the crude ether is refined to obtain a finished product through post-treatment, the prepared polyether polyol has better fluidity and is suitable for full-water foaming, the adhesive force with a pipe wall (wall and other attachments) is enhanced during foaming, and the foamed product has increased toughness, is not easy to tear and is not crisp; the size stability of the manufactured product is better, and the product is not deformed; has certain flame retardant effect; the heat conductivity coefficient is low, and the heat preservation effect is better; because the initiator introduces alcohols containing halogen, the initiator is a reactive flame retardant and is matched with an external additive flame retardant for use, the flame retardant property is greatly improved; the construction process is simple, and the method has wide application prospect.
Preferably, the halohydrin is tribromoneopentyl alcohol, dibromoneopentyl glycol, bromoneopentyl glycol, phosphorus bromine-containing polyol, polyol-chlorobutylene oxide adduct, or the like.
Preferably, the halohydrin is bromoneopentyl glycol.
Preferably, the low molecular weight polyol is one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol or triethylene glycol.
Preferably, the low molecular weight polyol is diethylene glycol and propylene glycol.
Preferably, the mass ratio of the diethylene glycol to the propylene glycol is 1:1 to 5.
Preferably, the alkali metal salt catalyst is potassium hydroxide, the addition amount of the potassium hydroxide accounts for 2.0-4.0% by mass of the whole reaction system, and the whole reaction system refers to the total addition amount of the composite initiator, the catalyst and the epoxide.
Preferably, the mass ratio of the sucrose, the halogenated alcohol, the low-molecular-weight polyol, the phenolic resin and the oil is 342: 15-50: 25-90: 20-30: 200 to 300.
Preferably, the grease is palm oil, the mass percentage of the grease in the whole reaction system is 14-21%, and the whole reaction system refers to the total added mass of the composite initiator, the catalyst and the epoxide.
Preferably, in the mixture of propylene oxide and ethylene oxide in the step 2, the mass ratio of propylene oxide to ethylene oxide is 1: 0.2 to 1.
The process can obtain the all-water foaming hard foam polyether polyol product with the hydroxyl value of 310-350 mgKOH/g and the viscosity (25 ℃) of 800-1100 mPa.s, and the prepared product has low viscosity of the prepared combined material, better fluidity, good mold filling property when foaming a foam product, certain flame retardant effect and suitability for the all-water foaming process.
Advantageous effects
Aiming at the defects of high polyether viscosity, high cost, unstable product quality, poor flame retardant effect and the like existing in the application of the all-water foaming hard foam polyether in the current market, the invention prepares a brand-new all-water foaming hard flame retardant polyether polyol by optimizing the formula of an initiator and simultaneously mixing and polymerizing a proper amount of EO (ethylene oxide). The method takes sucrose, low molecular weight polyol, halohydrin, phenolic resin and grease as initiators and alkali metal salt as a catalyst, and a section of propylene oxide is introduced for reaction; after the reaction is finished, the mixture of the epoxypropane ring and the ethylene oxide is introduced for mixed polymerization reaction, and the crude ether is refined to obtain the finished product. The prepared polyether polyol has better fluidity, is suitable for a full-water foaming process, enhances the adhesive force with a pipe wall (attachments such as a wall) during foaming, and increases the toughness of a foamed product, so that the foamed product is not easy to tear and crisp; the size stability of the manufactured product is better, and the product is not deformed; the heat conductivity coefficient is low, and the heat preservation and flame retardant effects are better; because the initiator introduces alcohols containing halogen, the initiator is a reactive flame retardant and is matched with an external additive flame retardant for use, the flame retardant property is greatly improved; the construction process is simple, and the method has wide application prospect. The hydroxyl value of the prepared all-water foaming hard foam polyether polyol product is 310-350 mgKOH/g, and the viscosity (25 ℃) is 800-1100 mPa.s.
The hard foam flame-retardant polyether polyol for full water foaming prepared by the invention has low viscosity, the prepared composite material has low viscosity, and the foam product has good mold filling property when being foamed, and is suitable for the full water foaming process. In the synthesis process of the polyether polyol, the proportion of the epoxide is relatively low, and a certain amount of ethylene oxide (the market price of the ethylene oxide is lower than that of the propylene oxide) is polymerized, so that the raw material cost is reduced; because the halogenated alcohol, the phenolic resin and the grease are introduced into the initiator, the foamed product has a certain flame retardant effect, the compressive strength is improved, and the toughness is good; in the polymerization process, ethylene oxide is mixed and polymerized, the bonding strength of the foam product is improved, the raw material cost is reduced, the hydrophilicity of polyether polyol is improved, and the stability of the polyether composite material is improved.
The preparation method has the advantages of simple operation of the process and high production efficiency; the hard foam flame-retardant polyether product for all-water foaming, which is obtained by the preparation method, has moderate hydroxyl value, low viscosity, low cost and good compatibility with water; the foamed product has high compression strength, good dimensional stability, strong binding power with a heat insulation system, low foam heat conductivity coefficient and good toughness; the polyurethane foam plastic prepared by the method has narrower density distribution, higher strength, good dimensional stability and bonding strength and lower heat conductivity coefficient; has certain flame retardant effect, and is particularly suitable for all-water foaming heat-insulating grinding pipelines and other heat-insulating fields. The product has uniform molecular weight distribution, stable product performance and no delamination under high and low temperature environments; the product has high activity, the foaming and rising speed in winter is not weakened, and the method is suitable for environmental construction all the year round; meanwhile, the cost is lower than that of similar products in the current market, so that the method is favorable for market popularization and application.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Comparative example
Adding 342g of cane sugar, 120g of diethylene glycol, 50g of propylene glycol and 7g of potassium hydroxide into a 5L autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil pipe) and a pressure sensor, replacing 3 times with nitrogen, heating, starting a vacuum pump to perform vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, maintaining the reaction temperature in the autoclave at 80-110 ℃ by controlling the feeding speed of the propylene oxide and the temperature control device, keeping the pressure in the autoclave at 0.1-0.4 MPa until the propylene oxide is added to 1600g, and curing for 3 hours after the reaction after the feeding is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
The performance indexes of the synthesized full water foaming hard foam polyether polyol are shown in the table 1.
Example 1
Adding 342g of cane sugar, 30g of bromo-neopentyl glycol, 20g of diethylene glycol, 30g of propylene glycol, 22g of phenolic resin, 225g of palm oil and 7g of potassium hydroxide into a 5L high-pressure autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, replacing 3 times with nitrogen, heating, starting a vacuum pump, carrying out vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, the reaction temperature in the kettle is maintained at 80-110 ℃ and the pressure is in the range of 0.1-0.4 MPa by controlling the feeding speed of the propylene oxide and the temperature control device until the propylene oxide is added to 1200g, and adding 300g of a mixture of propylene oxide and ethylene oxide (180 g of propylene oxide and 120g of ethylene oxide), controlling the temperature to be 80-110 ℃ and the pressure in the kettle to be 0.1-0.4 MPa, and curing for 3 hours after the reaction after the feeding is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
The performance indexes of the synthesized full water foaming hard foam polyether polyol are shown in the table 1.
Example 2
Adding 342g of cane sugar, 30g of bromo-neopentyl glycol, 20g of diethylene glycol, 30g of propylene glycol, 225g of palm oil and 7g of potassium hydroxide into a 5L high-pressure autoclave provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, replacing 3 times with nitrogen, heating, starting a vacuum pump, carrying out vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, the reaction temperature in the kettle is maintained at 80-110 ℃ and the pressure is in the range of 0.1-0.4 MPa by controlling the feeding speed of the propylene oxide and the temperature control device until the propylene oxide is added to 1200g, and adding 300g of a mixture of propylene oxide and ethylene oxide (180 g of propylene oxide and 120g of ethylene oxide), controlling the temperature to be 80-110 ℃ and the internal pressure of the kettle to be 0.1-0.4 MPa, and curing for 3 hours after the reaction after the feeding is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
The performance indexes of the synthesized full water foaming hard foam polyether polyol are shown in the table 1.
Example 3
Adding 342g of cane sugar, 30g of bromo-neopentyl glycol, 20g of diethylene glycol, 30g of propylene glycol, 22g of phenolic resin, 225g of palm oil and 7g of potassium hydroxide into a 5L high-pressure kettle provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil pipe) and a pressure sensor, replacing with nitrogen for 3 times, heating, starting a vacuum pump to perform vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, maintaining the reaction temperature in the kettle at 80-110 ℃ and the pressure at 0.1-0.4 MPa by controlling the feeding speed and the temperature control device of the propylene oxide until the propylene oxide is added to 1500g, and curing for 3 hours after the reaction is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
The performance indexes of the synthesized full water foaming hard foam polyether polyol are shown in the table 1.
Example 4
Adding 342g of cane sugar, 15g of tribromoneopentyl alcohol, 10g of diethylene glycol, 15g of propylene glycol, 30g of phenolic resin, 200g of palm oil and 7g of potassium hydroxide into a 5L high-pressure kettle provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil) and a pressure sensor, replacing for 3 times by nitrogen, heating, starting a vacuum pump, carrying out vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, the reaction temperature in the kettle is maintained at 80-110 ℃ and the pressure is in the range of 0.1-0.4 MPa by controlling the feeding speed of the propylene oxide and the temperature control device until the propylene oxide is added to 1350g, and then adding 150g of a mixture of propylene oxide and ethylene oxide (100 g of propylene oxide and 50g of ethylene oxide), controlling the temperature to be 80-110 ℃ and the pressure in the kettle to be 0.1-0.4 MPa, and curing for 3 hours after the reaction after the feeding is finished. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
Example 5
Adding 342g of cane sugar, 50g of dibromo neopentyl glycol, 20g of diethylene glycol, 70g of propylene glycol, 20g of phenolic resin, 300g of palm oil and 7g of potassium hydroxide into a 5L high-pressure kettle provided with a stirrer, a meter, a heating temperature control device, a cooling device (comprising an outer jacket and an inner coil pipe) and a pressure sensor, replacing 3 times with nitrogen, heating, starting a vacuum pump to perform vacuum dehydration at 100-105 ℃ for 3 hours, cooling to 80 ℃, starting to continuously dropwise add propylene oxide, keeping the reaction temperature in the kettle at 80-110 ℃ and the pressure within the range of 0.1-0.4 MPa by controlling the feeding speed and the temperature control device of the propylene oxide until the propylene oxide is added to 1200g, adding 300g of a mixture of the propylene oxide and the ethylene oxide (150 g of the propylene oxide and 150g of the ethylene oxide), controlling the temperature at 80-110 ℃ and the pressure in the kettle at 0.1-0.4 MPa, after the completion of the feeding, the reaction was aged for 3 hours. And adding water and acid to the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the full-water foamed hard foam polyether polyol.
TABLE 1 all water blown rigid foam polyether polyol Performance index
Figure BDA0002241503650000071
It can be seen from table 1 that the rigid foam flame-retardant polyether polyol product for all-water foaming prepared in the embodiment of the invention has low viscosity and is suitable for all-water foaming process.
The performance comparison test of the synthesized all-water foaming hard foam polyether polyol is as follows:
100 parts by mass of the polyether polyols prepared in examples 1 to 3 and comparative example, 2.5 parts by mass of a foam stabilizer DC-193 from American gas Co, 1.5 parts by mass of a N, N dimethylcyclohexylamine catalyst and 4.0 parts by mass of water were mixed uniformly to prepare a composite material, and the composite material was mixed with PM200 from Wanhua chemical group Co., Ltd in a mass ratio of 1:1.10 to prepare a foam having properties shown in Table 2
TABLE 2 foam Properties
Figure BDA0002241503650000081
As can be seen from the data in Table 2, the foamed product prepared from the hard foam flame-retardant polyether polyol for full-water foaming prepared in example 1 of the invention has moderate density, low thermal conductivity, high compressive strength and bonding strength and good toughness.
As can be seen from the data in Table 2, the foamed article prepared from the rigid foam flame-retardant polyether polyol for full-water foaming prepared in example 2 of the present invention has moderate density and low thermal conductivity, and has reduced compressive strength and good toughness due to the removal of the phenolic resin from the initiator.
As can be seen from the data in Table 2, the foamed article prepared from the rigid foam flame-retardant polyether polyol for full-water foaming prepared in example 3 of the present invention has moderate density, low thermal conductivity, high compressive strength, reduced bonding strength due to the absence of ethylene oxide in the polymeric epoxy compound, and good toughness.
As can be seen from the data in Table 2, the foamed products foamed by the hard foam flame-retardant polyether polyol for full water foaming prepared by the examples 1, 2 and 3 of the invention have improved oxygen index due to the introduction of the halohydrin into the initiator, which indicates that the foamed products foamed by the polyether polyol prepared by the invention have certain flame-retardant effect.
As can be seen from the data in Table 2, the foam product foamed by the hard foam flame-retardant polyether polyol for full water foaming prepared by the comparative example has moderate density and higher heat conductivity coefficient, and because the initiator does not contain phenolic resin and grease, the compressive strength of the product is reduced, and the toughness is poor; the bond strength is reduced due to the absence of ethylene oxide in the polymeric epoxy.
As can be seen from the data in tables 1 and 2, the rigid foam flame-retardant polyether polyol for all-water foaming prepared by the embodiment of the invention has low viscosity, the prepared composite material has low viscosity, and the foam product has good mold filling property and is suitable for all-water foaming process. Because the proportion of the epoxide in the polyether polyol is relatively low, and a certain amount of ethylene oxide is polymerized (the market price of the ethylene oxide is lower than that of the propylene oxide), the raw material cost is reduced; because the halogenated alcohol, the phenolic resin and the grease are introduced into the initiator, the foamed product has a certain flame retardant effect, the compressive strength is improved, and the toughness is good; in the polymerization process, ethylene oxide is mixed and polymerized, the bonding strength of the foam product is improved, the raw material cost is reduced, the hydrophilicity of polyether polyol is improved, and the stability of the polyether composite material is improved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (9)

1. A preparation method of hard foam flame-retardant polyether polyol for full water foaming is characterized by comprising the following steps:
(1) feeding and pretreating: adding sucrose, halohydrin, low-molecular-weight polyol, phenolic resin and grease into a reaction kettle, then adding an alkali metal salt catalyst, replacing for 3-5 times with nitrogen, then heating to 100-105 ℃, and performing vacuum dehydration until the water content of materials in the kettle is within 0.5% (wt);
(2) polymerization reaction: controlling the temperature in the reaction kettle to be 80-85 ℃, then starting to dropwise add the epoxypropane, and controlling the temperature in the reaction kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the process of dropwise adding the epoxypropane; dropwise adding propylene oxide to 80-90% of the total added mass of the propylene oxide, mixing the residual propylene oxide and ethylene oxide, dropwise adding the mixture of the propylene oxide and the ethylene oxide into a reaction kettle, controlling the temperature in the kettle to be 80-110 ℃ and the pressure to be 0.1-0.4 MPa in the dropwise adding process, and then curing for 1.5-3.5 hours;
(3) and (3) post-treatment: adding water and acid into the cured product for neutralization, adding an adsorbent, vacuumizing, dehydrating, degassing, and performing filter pressing to obtain the product, namely the hard foam polyether polyol for full-water foaming.
2. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the halogenated alcohol is one or more of tribromoneopentyl alcohol, dibromo neopentyl glycol, bromo neopentyl glycol, phosphorus bromine-containing polyol and polyol-epoxy chlorobutane addition compound.
3. The low molecular weight polyol of claim 1 being one or more of glycerol, propylene glycol, diethylene glycol, ethylene glycol, dipropylene glycol, or triethylene glycol.
4. The method for preparing the hard foam flame-retardant polyether polyol for all-water foaming according to claim 3, wherein the method comprises the following steps: the low molecular weight polyol is diethylene glycol and propylene glycol.
5. The method for preparing the rigid foam flame-retardant polyether polyol for all-water foaming according to claim 4, wherein the rigid foam flame-retardant polyether polyol comprises the following steps: the mass ratio of the diethylene glycol to the propylene glycol is 1:1 to 5.
6. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the alkali metal salt catalyst is potassium hydroxide, and the mass percentage of the catalyst added in the whole reaction system is 2.0-4.0%.
7. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the mass ratio of the sucrose to the halogenated alcohol to the low-molecular-weight polyol to the phenolic resin to the grease is 342: 15-50: 25-90: 20-30: 200 to 300.
8. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: the oil is palm oil, and the oil accounts for 14-21% of the whole reaction system by mass.
9. The preparation method of the hard foam flame-retardant polyether polyol for all-water foaming according to claim 1, characterized in that: in the mixture of propylene oxide and ethylene oxide in the step 2, the mass ratio of propylene oxide to ethylene oxide is 1: 0.2 to 1.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111286019A (en) * 2020-02-24 2020-06-16 滨化集团股份有限公司 Preparation method of high-bonding-force rigid polyether polyol for foaming
CN111471170A (en) * 2020-04-22 2020-07-31 山东福瑞斯新材料科技有限公司 Preparation process of environment-friendly polyurethane all-water composite material
CN112552503A (en) * 2020-12-15 2021-03-26 句容宁武新材料股份有限公司 Preparation method of bronopol reaction type flame-retardant polyether polyol
CN112646161A (en) * 2020-12-14 2021-04-13 山东一诺威新材料有限公司 Full sucrose type flame-retardant polyether polyol and preparation method thereof
CN113698587A (en) * 2021-09-08 2021-11-26 航锦科技股份有限公司 Preparation method of hard foam polyether polyol
CN115246919A (en) * 2021-11-26 2022-10-28 佳化化学科技发展（上海）有限公司 Polyurethane grouting material and preparation method and application thereof
CN115246917A (en) * 2021-10-22 2022-10-28 佳化化学科技发展（上海）有限公司 All-water polyurethane rigid foam with anti-crisp property and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030158448A1 (en) * 2002-01-30 2003-08-21 Lassila Kevin Rodney Glycidyl ether-capped acetylenic diol ethoxylate surfactants
US20060175005A1 (en) * 2005-02-08 2006-08-10 Sawant Suresh G Compositions and methods of making compositions exhibiting fuel resistance
CN102911334A (en) * 2012-11-14 2013-02-06 滕州市华海新型保温材料有限公司 B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030158448A1 (en) * 2002-01-30 2003-08-21 Lassila Kevin Rodney Glycidyl ether-capped acetylenic diol ethoxylate surfactants
US20060175005A1 (en) * 2005-02-08 2006-08-10 Sawant Suresh G Compositions and methods of making compositions exhibiting fuel resistance
CN102911334A (en) * 2012-11-14 2013-02-06 滕州市华海新型保温材料有限公司 B1-grade high-fire-retardant low-smoke-generation rigid polyurethane foam

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
化学工业出版社组织编写: "《中国化工产品大全》", 31 January 2005, 化学工业出版社组织编写 *
张付利: "《有机化学》", 28 February 2018, 河南大学出版社 *
王宝瑄: "《化合物命名词典》", 31 December 1992, 上海辞书出出版社 *

Cited By (9)

* Cited by examiner, † Cited by third party
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CN111286019A (en) * 2020-02-24 2020-06-16 滨化集团股份有限公司 Preparation method of high-bonding-force rigid polyether polyol for foaming
CN111471170A (en) * 2020-04-22 2020-07-31 山东福瑞斯新材料科技有限公司 Preparation process of environment-friendly polyurethane all-water composite material
CN112646161A (en) * 2020-12-14 2021-04-13 山东一诺威新材料有限公司 Full sucrose type flame-retardant polyether polyol and preparation method thereof
CN112646161B (en) * 2020-12-14 2022-11-29 山东一诺威新材料有限公司 Full sucrose type flame-retardant polyether polyol and preparation method thereof
CN112552503A (en) * 2020-12-15 2021-03-26 句容宁武新材料股份有限公司 Preparation method of bronopol reaction type flame-retardant polyether polyol
CN113698587A (en) * 2021-09-08 2021-11-26 航锦科技股份有限公司 Preparation method of hard foam polyether polyol
CN115246917A (en) * 2021-10-22 2022-10-28 佳化化学科技发展（上海）有限公司 All-water polyurethane rigid foam with anti-crisp property and preparation method and application thereof
CN115246919A (en) * 2021-11-26 2022-10-28 佳化化学科技发展（上海）有限公司 Polyurethane grouting material and preparation method and application thereof
CN115246919B (en) * 2021-11-26 2023-12-22 佳化化学科技发展（上海）有限公司 Polyurethane grouting material and preparation method and application thereof

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