CN114395120B - Preparation method of flame-retardant high-temperature-resistant polyether polyol - Google Patents
Preparation method of flame-retardant high-temperature-resistant polyether polyol Download PDFInfo
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- CN114395120B CN114395120B CN202111578476.XA CN202111578476A CN114395120B CN 114395120 B CN114395120 B CN 114395120B CN 202111578476 A CN202111578476 A CN 202111578476A CN 114395120 B CN114395120 B CN 114395120B
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 60
- 229920000570 polyether Polymers 0.000 title claims abstract description 60
- 229920005862 polyol Polymers 0.000 title claims abstract description 43
- 150000003077 polyols Chemical class 0.000 title claims abstract description 43
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005086 pumping Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 8
- 235000019792 magnesium silicate Nutrition 0.000 claims description 8
- 239000000391 magnesium silicate Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000007142 ring opening reaction Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000006260 foam Substances 0.000 abstract description 13
- 238000004321 preservation Methods 0.000 abstract description 7
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 4
- 239000011496 polyurethane foam Substances 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 small molecule alcohols Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/5063—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- 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
- C08G65/2696—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
-
- 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
Abstract
The invention belongs to the technical field of polyether polyol preparation, and particularly relates to a preparation method of flame-retardant high-temperature-resistant polyether polyol. The method comprises the following steps: putting the composite initiator into a reaction kettle, sealing, pumping acetic anhydride, heating and opening the ring; adding an alkali metal catalyst, sealing, continuously dropwise adding propylene oxide for polymerization reaction for the first time, heating after the reaction is finished, continuously dropwise adding the rest propylene oxide for polymerization reaction for the second time, and obtaining crude polyether; removing unreacted monomers, and performing aftertreatment to obtain a polyether polyol product; the composite initiator is a mixture of melamine initiator and tetrahydrofuran or a mixture of melamine initiator, tetrahydrofuran and micromolecular alcohol initiator. The polyether polyol prepared by the invention is used for preparing polyurethane foam, not only can improve the stability of a foam structure, but also can greatly improve the thermal stability of a foam body, and also has certain flame retardance, and is mainly applied to the field of pipeline heat preservation at high temperature for a long time.
Description
Technical Field
The invention belongs to the technical field of polyether polyol preparation, and particularly relates to a preparation method of flame-retardant high-temperature-resistant polyether polyol.
Background
Polyurethane foam plastic is widely applied to the heat preservation fields of town heat supply, central air conditioning, building walls and the like due to the advantages of excellent heat insulation performance, extremely low moisture absorption and moisture resistance, convenient forming performance and the like.
The polyurethane heat-insulating layer is widely applied to the fields of town heat supply, central air conditioning, building walls, industrial chemical industry and the like due to the characteristics of low volume weight, high compressive strength and the like. The polyurethane heat-insulating material is a rigid foam plastic with functions of water resistance, heat preservation, heat insulation and the like, which is formed by mixing and reacting a component A and a component B, and is also called polyurethane rigid foam, wherein the component A is a combined polyether polyol commonly called white material; the component B is isocyanate commonly known as black material. When A, B components are mixed, chemical reaction starts to occur, and a heating phenomenon is accompanied, so that gas is generated and heated to expand, and a foam porous structure is formed.
In the urban heat supply field, polyurethane direct-buried heat preservation pipes are mostly adopted at present to carry out hot water medium delivery. Through detection accumulation and investigation in the heat supply field for many years, the serious carbonization problem of the heat insulation layer of the polyurethane direct-buried heat insulation pipe in many areas is found. After the polyurethane is carbonized, on one hand, the 'three-in-one' structure of the directly buried heat preservation pipe fails, and the pipe is free to slide in the process of thermal expansion and contraction, so that the compensator, the valve, the pipe and the like are broken and damaged; on the other hand, after polyurethane carbonization, water outside the heat preservation pipe enters the surface of the working steel pipe, serious corrosion occurs to the pipeline, and serious corrosion perforation risks occur to the pipeline.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of flame-retardant high-temperature-resistant polyether polyol, and the prepared polyether polyol is used for preparing polyurethane foam, so that the stability of a foam structure can be improved, the thermal stability of a foam body can be greatly improved, and the flame-retardant high-temperature-resistant polyether polyol has certain flame retardance.
The preparation method of the flame-retardant high-temperature-resistant polyether polyol comprises the following steps:
putting the composite initiator into a reaction kettle, performing sealing kettle operation, pumping acetic anhydride after nitrogen replacement, heating and ring opening; adding an alkali metal catalyst, performing sealing kettle operation, replacing nitrogen, controlling the temperature in a polymerization kettle, continuously dropwise adding propylene oxide for the first time to perform polymerization reaction, heating up after the reaction is finished, continuously dropwise adding the rest propylene oxide for the second time to perform polymerization reaction, and obtaining crude polyether; removing unreacted monomers, and performing aftertreatment to obtain a polyether polyol product;
the composite initiator is a mixture of melamine initiator and tetrahydrofuran or a mixture of melamine initiator, tetrahydrofuran and micromolecular alcohol initiator.
Wherein:
the first continuous dripping propylene oxide accounts for 20-45% of the total propylene oxide.
The melamine initiator is one or two of melamine or benzomelamine.
The micromolecular alcohol initiator is one or more of glycerol, diethylene glycol, trimethylolpropane or propylene glycol.
The mass ratio of the solid liquid of the composite initiator is 1:3.85-5.55. The solid-liquid ratio is too large, the viscosity is large, stirring is stopped, and even if the stirring is not stopped, a lot of solid raw materials are not reacted finally. If the solid-to-liquid ratio is too small, most tetrahydrofuran does not participate in the reaction and is removed, so that waste is caused.
The above solids refer to: melamine, benzomelamine, catalyst, liquid refers to tetrahydrofuran, small molecule alcohols.
The consumption of the acetic anhydride is 0.05-0.2% of the crude polyether.
The heating ring-opening specifically comprises the following steps: heating to 50-70 ℃ for reaction for 4-8 hours for ring opening.
The alkali metal catalyst is one or two of potassium methoxide or solid KOH.
The dosage of the alkali metal catalyst is 0.3-0.5% of the crude polyether.
Preferably, the preparation method of the flame-retardant high-temperature-resistant polyether polyol comprises the following steps of:
1) Putting the composite initiator into a reaction kettle, performing sealing kettle operation, pumping acetic anhydride after nitrogen replacement, heating and ring opening;
2) Adding an alkali metal catalyst, performing sealing kettle operation, replacing nitrogen, controlling the temperature in a polymerization kettle to be 75-85 ℃, continuously dropwise adding propylene oxide for the first time to perform polymerization reaction, controlling the pressure in the kettle to be 0MPa to 0.2MPa, and curing for 0.5-1h after the dropwise adding is finished;
3) Heating to 90-110 ℃, continuously dripping the rest propylene oxide for a second time to perform polymerization reaction, controlling the pressure in the kettle to be 0-0.2 MPa, curing for 3-5h after the dripping is finished, and obtaining crude polyether;
4) Controlling the temperature in the kettle at 100-140 ℃, vacuumizing, controlling the pressure in the kettle at-0.08 to-0.09 MPa, and removing unreacted propylene oxide and tetrahydrofuran monomers;
5) Reducing the temperature in the reaction kettle to 75-85 ℃, adding phosphoric acid and water, stirring, adding magnesium silicate, heating to 100-110 ℃, vacuumizing and dehydrating to control the pressure in the reaction kettle to be minus 0.08-minus 0.09MPa, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol product.
The addition of phosphoric acid is 0.6-0.7% of crude polyether, the addition of water is 7-8% of crude polyether, and the addition of magnesium silicate is 0.15-0.2% of crude polyether.
The average functionality of the polyether polyol product is 3-5, the hydroxyl value is 360-400mg/KOH, and the viscosity is 500-3000 mPa.s.
The flame-retardant high-temperature-resistant polyether polyol is mainly applied to the field of pipeline heat preservation at high temperature for a long time.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts reasonable collocation initiator, and increases rigidity and flame-retardant effect by introducing six-membered triazine ring and benzene ring in melamine or benzomelamine, so as to stabilize foam structure and greatly improve thermal stability of foam.
2. The drastic change in temperature difference may lead to deterioration in the stability of the crosslinked structure of the foam. The severe internal stress in the sharply warmed environment can lead to fracture of the crosslinked structure, while the high temperature can lead to partial dehydration and carbonization of the foam. According to the invention, the intramolecular internal stress is counteracted by introducing the tetrahydrofuran low-crosslinking-degree long-chain structure, so that the phenomenon of fracture carbonization in the environment with severe temperature change can be avoided.
3. The tetrahydrofuran in the invention can be used as a solvent to reduce solid-liquid ratio, prevent stirring stop, uniformly transfer heat, dissolve melamine or benzomelamine, and can be used as a monomer for mixing polymerization with propylene oxide to obtain polyether to enhance toughness.
Detailed Description
The invention is further described below in connection with examples, which are not intended to limit the practice of the invention.
The starting materials used in the examples are all commercially available, except as specified.
Example 1
50g of melamine, 250g of benzomelamine, 1100g of tetrahydrofuran and 60g of glycerol are put into a reaction kettle, then the reaction kettle is sealed, nitrogen is replaced for three times, 1.23g of acetic anhydride is pumped in, the temperature is raised to 70 ℃, the pressure is stamped to 0.2MPa, and the reaction is carried out for 4 hours. After the temperature is reduced to normal temperature, 7.90g of solid KOH catalyst is added into the kettle, then the sealing kettle is carried out, nitrogen is replaced for three times, the temperature in the polymerization kettle is controlled to be 75-85 ℃, propylene oxide is continuously added dropwise into the polymerization kettle, the feeding speed is controlled to be lower than 0.2MPa, the first part of 150g of propylene oxide is completely added dropwise, and the reaction kettle is cured for 0.5h. Heating to 110 ℃, continuously dripping 200g of propylene oxide into the second part, controlling the pressure below 0.2MPa in the process until the propylene oxide is completely dripped, and curing for 3 hours to obtain crude polyether. Controlling the temperature in the kettle to be 110-115 ℃, vacuumizing, controlling the pressure in the kettle to be-0.08-0.09 MPa, and removing unreacted epoxypropane, tetrahydrofuran and other gases for 1h. Reducing the temperature in the reaction kettle to 80 ℃, adding 12.28g of phosphoric acid and 140.4g of water, stirring for 1h, adding 3.51g of magnesium silicate, heating to 100-110 ℃, vacuumizing, dehydrating, controlling the pressure in the kettle to be between-0.08 and-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number 363 and a viscosity 968 was obtained.
Example 2
187g of benzomelamine and 936g of tetrahydrofuran are put into a reaction kettle, then the reaction kettle is sealed, nitrogen is replaced for three times, 1.4g of acetic anhydride is pumped in, the temperature is raised to 70 ℃, the pressure is increased to 0.2MPa, and the reaction is carried out for 6 hours. And (3) after the temperature is reduced to normal temperature, opening the kettle, adding 7g of solid KOH catalyst, then carrying out sealing kettle operation, replacing nitrogen for three times, controlling the temperature in the polymerization kettle at 75-85 ℃, continuously dropwise adding propylene oxide in the polymerization kettle, controlling the pressure in the kettle at a feeding speed below 0.2MPa, completely dropwise adding 85g of propylene oxide in the first part, and curing for 0.5h. And heating to 110 ℃, continuously dropwise adding 190g of propylene oxide into the second part, ensuring that the pressure is controlled below 0.2MPa in the process until the propylene oxide is completely dropwise added, and curing for 3 hours to obtain crude polyether. Controlling the temperature in the kettle to be 110-115 ℃, vacuumizing, controlling the pressure in the kettle to be-0.08-0.09 MPa, and removing unreacted epoxypropane, tetrahydrofuran and other gases for 1h. Reducing the temperature in the reaction kettle to 75 ℃, adding 9.85g of phosphoric acid and 112.5g of water, stirring for 1h, adding 2.81g of magnesium silicate, heating to 100-110 ℃, vacuumizing, dehydrating, controlling the pressure in the kettle to be between-0.08 and-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 385 and a viscosity of 2249 was obtained.
Example 3
200g of benzomelamine, 908g of tetrahydrofuran and 55g of diethylene glycol are put into a reaction kettle, then the reaction kettle is sealed, nitrogen is replaced for three times, 0.79g of acetic anhydride is pumped in, the temperature is raised to 50 ℃, the pressure is stamped to 0.2MPa, and the reaction is carried out for 8 hours. After the temperature is reduced to normal temperature, opening the kettle, adding 5.52g of potassium methoxide catalyst, then carrying out the operation of sealing the kettle, replacing nitrogen for three times, controlling the temperature in the kettle of the polymerization kettle to be 75-85 ℃, continuously dropwise adding propylene oxide, controlling the feeding speed to be less than 0.2MPa, controlling the pressure in the kettle to be lower than 0.2MPa, and curing for 0.5h after the first part 185g of propylene oxide is completely dropwise added. Heating to 110 ℃, continuously dropwise adding 230g of propylene oxide in the second part, controlling the pressure below 0.2MPa in the process until the propylene oxide is completely dropwise added, and curing for 3 hours to obtain crude polyether. Controlling the temperature in the kettle to be 110-115 ℃, vacuumizing, controlling the pressure in the kettle to be-0.08-0.09 MPa, and removing unreacted epoxypropane, tetrahydrofuran and other gases for 1h. Reducing the temperature in the reaction kettle to 85 ℃, adding 9.85g of phosphoric acid and 112.5g of water, stirring for 1h, adding 2.81g of magnesium silicate, heating to 100-110 ℃, vacuumizing, dehydrating, controlling the pressure in the kettle to be between-0.08 and-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 398 and a viscosity of 2898 was obtained.
Example 4
200g of melamine, 1020g of tetrahydrofuran and 80g of diethylene glycol are put into a reaction kettle, then the reaction kettle is sealed, nitrogen is replaced for three times, 2.35g of acetic anhydride is pumped in, the temperature is raised to 70 ℃, the pressure is raised to 0.2MPa, and the reaction is carried out for 8 hours. After the temperature is reduced to normal temperature, opening the kettle, adding 10.57g of solid KOH catalyst, then carrying out the operation of sealing the kettle, replacing nitrogen for three times, controlling the temperature in the kettle of the polymerization kettle to be 75-85 ℃, continuously dropwise adding propylene oxide, controlling the pressure in the kettle to be below 0.2MPa at the feeding speed, and curing for 0.5h after the first part of 250g of propylene oxide is completely dropwise added. Heating to 110 ℃, continuously dripping 800g of propylene oxide into the second part, controlling the pressure below 0.2MPa in the process until the propylene oxide is completely dripped, and curing for 3 hours to obtain the crude polyether. Controlling the temperature in the kettle to be 110-115 ℃, vacuumizing, controlling the pressure in the kettle to be-0.08-0.09 MPa, and removing unreacted epoxypropane, tetrahydrofuran and other gases for 1h. Reducing the temperature in the reaction kettle to 80 ℃, adding 16.45g of phosphoric acid and 188g of water, stirring for 1h, adding 4.7g of magnesium silicate, heating to 100-110 ℃, vacuumizing, dehydrating, controlling the pressure in the kettle to be between-0.08 and-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 374 and a viscosity of 1808 was obtained.
Comparative example 1
300g of glycerin and 4.27g of solid KOH4.27g are put into a reaction kettle, the temperature is raised to 100 ℃ by the operation of sealing the kettle, and the water content of materials in the kettle is controlled to be lower than 0.1% by the operation of vacuumizing and dehydrating. Controlling the temperature in the polymerization kettle to be 100-105 ℃, continuously dropwise adding propylene oxide, controlling the actual temperature of materials to react between 100-105 ℃ in the process, controlling the pressure in the kettle to be less than 0.4MPa by the feeding speed, and curing for 3h after 1125g of propylene oxide is completely dropwise added. Controlling the temperature in the kettle to be 110-115 ℃, vacuumizing, controlling the pressure in the kettle to be-0.08-0.09 MPa, and removing unreacted propylene oxide monomer for 1h. Reducing the temperature in the reaction kettle to 80 ℃, adding 9.97g of phosphoric acid and 114g of water, stirring for 1h, adding 2.85g of magnesium silicate, heating to 100-110 ℃, vacuumizing, dehydrating, controlling the pressure in the kettle to be between-0.08 and-0.09 MPa, timing for 4h, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol finished product. A polyether polyol having a hydroxyl number of 388 and a viscosity of 525 was obtained.
Comparative example 2
187g of benzomelamine, 80g of diethylene glycol and 7g of solid KOH catalyst are put into a reaction kettle, then the reaction kettle is sealed, nitrogen is replaced for three times, the temperature in the polymerization kettle is controlled to be 75-85 ℃, propylene oxide is continuously dripped into the reaction kettle, the feeding speed is controlled to be lower than 0.2MPa, the first part of 85g of propylene oxide is completely dripped into the reaction kettle, the pressure in the reaction kettle is 0.31MPa at the moment, the pressure is still maintained to be more than 0.3MPa after the internal pressure is 4 hours, the reaction is difficult to carry out, and a large amount of unreacted solid benzomelamine is found in the reaction kettle by opening the reaction kettle after pressure relief.
The polyether polyol prepared by the above examples and comparative examples is prepared from the flame-retardant and high-temperature-resistant material according to the components A and B with the isocyanate index of 1.05 in parts by weight.
And (3) a component A: weighing 100 parts of polyether polyol, 20 parts of tri (2-chloropropyl) phosphate, 1 part of PC-8 catalyst, 1.5 parts of water, 2 parts of silicone oil and 25 parts of foaming agent 141B, and uniformly mixing the weighed materials to obtain a product with qualified component A;
the component B is polyphenyl polymethylene polyisocyanate.
A, B components are mixed according to the cyanate index of 1.05 to prepare the flame-retardant high-temperature-resistant polyurethane foam, the central part of the foam is cut into uniform cubes, and each surface has no obvious cracks and cells. The mixture was placed in a forced air oven at 130℃for 100 days, and then taken out to test the compressive strength.
Table 1 experimental data analysis table for examples and comparative examples
As can be seen from Table 1, the invention can obviously improve the high temperature resistance of the foam, and obtain the polyether polyol for the high temperature pipeline, which has good strength and low viscosity.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (9)
1. A preparation method of flame-retardant high-temperature-resistant polyether polyol is characterized by comprising the following steps: the method comprises the following steps:
putting the composite initiator into a reaction kettle, performing sealing kettle operation, pumping acetic anhydride after nitrogen replacement, heating and ring opening; adding an alkali metal catalyst, performing sealing kettle operation, replacing nitrogen, controlling the temperature in a polymerization kettle, continuously dropwise adding propylene oxide for the first time to perform polymerization reaction, heating up after the reaction is finished, continuously dropwise adding the rest propylene oxide for the second time to perform polymerization reaction, and obtaining crude polyether; removing unreacted monomers, and performing aftertreatment to obtain a polyether polyol product;
the compound initiator is a mixture of melamine initiator and tetrahydrofuran or a mixture of melamine initiator, tetrahydrofuran and micromolecular alcohol initiator, and the mass ratio of solid liquid of the compound initiator is 1:3.85-5.55.
2. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the melamine initiator is one or two of melamine or benzomelamine.
3. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the small molecular alcohol initiator is one or more of glycerol, diethylene glycol, trimethylolpropane or propylene glycol.
4. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the amount of acetic anhydride is 0.05-0.2% of the crude polyether.
5. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the heating open loop specifically comprises the following steps: heating to 50-70 ℃ for reaction for 4-8 hours for ring opening.
6. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the alkali metal catalyst is one or two of potassium methoxide or solid KOH.
7. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the alkali metal catalyst is used in an amount of 0.3 to 0.5% of the crude polyether.
8. The method for preparing the flame-retardant and high-temperature-resistant polyether polyol according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
1) Putting the composite initiator into a reaction kettle, performing sealing kettle operation, pumping acetic anhydride after nitrogen replacement, heating and ring opening;
2) Adding an alkali metal catalyst, performing sealing kettle operation, replacing nitrogen, controlling the temperature in a polymerization kettle to be 75-85 ℃, continuously dropwise adding propylene oxide for the first time to perform polymerization reaction, controlling the pressure in the kettle to be 0MPa to 0.2MPa, and curing for 0.5-1h after the dropwise adding is finished;
3) Heating to 90-110 ℃, continuously dripping the rest propylene oxide for a second time to perform polymerization reaction, controlling the pressure in the kettle to be 0-0.2 MPa, curing for 3-5h after the dripping is finished, and obtaining crude polyether;
4) Controlling the temperature in the kettle at 100-140 ℃, vacuumizing, controlling the pressure in the kettle at-0.08 to-0.09 MPa, and removing unreacted propylene oxide and tetrahydrofuran monomers;
5) Reducing the temperature in the reaction kettle to 75-85 ℃, adding phosphoric acid and water, stirring, adding magnesium silicate, heating to 100-110 ℃, vacuumizing and dehydrating to control the pressure in the reaction kettle to be minus 0.08-minus 0.09MPa, detecting that the water content is lower than 0.1%, discharging and filtering to obtain a qualified polyether polyol product.
9. The method for preparing a flame retardant, high temperature resistant polyether polyol according to any one of claims 1 to 8, wherein: polyether polyol product with average functionality of 3-5, hydroxyl number of 360-400mg/KOH and viscosity of 500-3000 mPa.s.
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