CN115109218A - Flame-retardant combined polyether and preparation method thereof - Google Patents
Flame-retardant combined polyether and preparation method thereof Download PDFInfo
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- CN115109218A CN115109218A CN202210777490.0A CN202210777490A CN115109218A CN 115109218 A CN115109218 A CN 115109218A CN 202210777490 A CN202210777490 A CN 202210777490A CN 115109218 A CN115109218 A CN 115109218A
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- polyether
- flame
- polyether polyol
- retardant
- polyol
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 161
- 229920000570 polyether Polymers 0.000 title claims abstract description 161
- 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 56
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920005862 polyol Polymers 0.000 claims abstract description 103
- 150000003077 polyols Chemical class 0.000 claims abstract description 103
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 54
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 33
- 239000003381 stabilizer Substances 0.000 claims abstract description 31
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229920002545 silicone oil Polymers 0.000 claims abstract description 20
- 238000004945 emulsification Methods 0.000 claims abstract description 14
- 238000013329 compounding Methods 0.000 claims abstract description 12
- FDVSPBLZPJMXFV-UHFFFAOYSA-N 2-[4-[[2-(5-chlorothiophen-2-yl)-5-ethyl-6-methylpyrimidin-4-yl]amino]phenyl]acetic acid Chemical compound CCC1=C(C)N=C(C=2SC(Cl)=CC=2)N=C1NC1=CC=C(CC(O)=O)C=C1 FDVSPBLZPJMXFV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 11
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000002156 mixing Methods 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 49
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 48
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000005303 weighing Methods 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 229920000877 Melamine resin Polymers 0.000 claims description 25
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 25
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 25
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 25
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 24
- 241001553178 Arachis glabrata Species 0.000 claims description 24
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 24
- 235000018262 Arachis monticola Nutrition 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 235000020232 peanut Nutrition 0.000 claims description 24
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 229910052987 metal hydride Inorganic materials 0.000 claims description 20
- 229920005903 polyol mixture Polymers 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000011033 desalting Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 10
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 150000004681 metal hydrides Chemical class 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 4
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011496 polyurethane foam Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920002323 Silicone foam Polymers 0.000 description 8
- 239000013514 silicone foam Substances 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003466 welding 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
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
-
- 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
-
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses flame-retardant combined polyether and a preparation method thereof, relates to combined polyether and flame-retardant combined polyether, is suitable for producing flame-retardant polyurethane materials, and belongs to the technical field of fine chemical engineering. The flame-retardant combined polyether is prepared by compounding polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol, A-33, stannous octoate, a silicone oil stabilizer, Tween 80, deionized water, cyclopentane and a compound microemulsion. The polyurethane foam is compounded by polyether polyol and polyester polyol with different hydroxyl values, and the produced polyurethane foam has proper hardness and is compatible in hardness and softness; the flame-retardant polyurethane composite material structurally has flame-retardant groups, so that the overall stability of the composite polyether is ensured, the phenomenon of phase separation of a flame retardant and other components cannot occur in the storage process, and the flame-retardant effect of the flame-retardant polyurethane produced and manufactured is better; the combined polyether has better uniformity and higher stability by adopting the technology of combining emulsification and micro-emulsification.
Description
Technical Field
The invention discloses flame-retardant combined polyether and a preparation method thereof, relates to combined polyether and flame-retardant combined polyether, is suitable for producing flame-retardant polyurethane materials, and belongs to the technical field of fine chemical engineering.
Background
Polyurethane is widely used in the fields of packaging, sealing, building external wall heat insulation and the like, but common polyurethane has no flame retardance, certain potential safety hazards exist in the using process, and particularly when the polyurethane is used as an external wall heat insulation material, the polyurethane heat insulation material is often ignited due to sparks caused by operations such as electric welding and the like. The composite polyether, commonly known as white material, is a raw material which must be used in the polyurethane manufacturing process, the polyurethane material can be obtained by utilizing the reaction of the composite polyether and isocyanate, and because the isocyanate is a single component and the composite polyether is a multi-component mixed system, the flame retardance of the polyurethane is usually realized by changing the composition of the composite polyether. The most common method is to add the flame retardant into the combined polyether, the method is simple and easy to operate, but the problem of poor compatibility of the flame retardant and other components exists, and the flame retardant is often separated out during the storage of the combined polyether, so that the later use is influenced. Therefore, the flame-retardant combined polyether and the preparation method thereof are necessary for structurally realizing the flame retardance of the combined polyether and effectively preventing the flame retardant from being separated from other components in the combined polyether.
Disclosure of Invention
The invention aims to provide flame-retardant combined polyether and a preparation method thereof.
The flame-retardant combined polyether is prepared from the following raw materials in parts by weight:
the polyether polyol A has a hydroxyl value of 410-450mgKOH/g, and the preparation process comprises the following steps: respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300-350: 8-12: 150-170: 100-200-260: 0.001-0.005: 0.0007-0.0015, uniformly mixing the melamine, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 100-160 ℃, slowly adding the propylene oxide, reacting for 30-50min under 0.4-0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09-0.11 MPa in vacuum to obtain the polyether polyol A.
The polyether polyol B has a hydroxyl value of 110-170mgKOH/g, and the preparation process comprises the following steps: processing the peanut shell into powder of 40-160 meshes, then weighing the peanut shell powder, glycol and concentrated sulfuric acid respectively according to the mass ratio of 100: 600-700: 15-25, uniformly mixing, heating to 140-160 ℃, treating for 60-90min, cooling with cold water to stop the reaction, and separating to obtain polyether polyol B.
The polyether polyol C has a hydroxyl value of 20-40mgKOH/g, and the preparation process comprises the following steps: respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double metal hydride complex catalyst MMC with a hydroxyl value of 52-60mgKOH/g according to the mass ratio of 100: 280-360: 3-7: 0.002-0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120-130 ℃, vacuumizing to-0.095 MPa-
Dehydrating at-0.099 MPa for 80-120min, closing vacuum, slowly dripping propylene oxide, continuing to react for 60-90min after dripping is finished, and then vacuumizing at 70-90 ℃ to remove unreacted residual monomers to obtain polyether polyol C.
The polyester polyol has a hydroxyl value of 360-480mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol.
The compound microemulsion is prepared by compounding C8-C9 alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 30-40: 480-.
The silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone cell stabilizer, the viscosity is 600-800mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 6.5-7.5.
The invention discloses a preparation method of flame-retardant combined polyether, which comprises the following steps:
(1) respectively weighing melamine, epoxypropane, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300-350: 8-12: 150-170: 100-120: 200-260: 0.001-0.005: 0.0007-0.0015, uniformly mixing the melamine, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 100-160 ℃, slowly adding epoxypropane, reacting for 30-50min under 0.4-0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09-0.11 MPa in vacuum to obtain polyether polyol A;
(2) processing the peanut shell into powder of 40-160 meshes, then respectively weighing the peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 600-700: 15-25, uniformly mixing, heating to 140-160 ℃, treating for 60-90min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double metal hydride complex catalyst MMC with a hydroxyl value of 52-60mgKOH/g according to the mass ratio of 100: 280 plus 360: 3-7: 0.002-0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120 plus 130 ℃, vacuumizing to-0.095-0.099 MPa, dehydrating for 80-120min, closing vacuum, slowly dripping propylene oxide, continuing to react for 60-90min after dripping is finished, vacuumizing at 70-90 ℃, and removing unreacted residual monomers to obtain polyether polyol C;
(4) weighing the following raw materials according to the formula:
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 20-40min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 60-90 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsify for 60-90min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
The flame-retardant combined polyether is prepared by compounding polyether polyol and polyester polyol with different hydroxyl values, and can ensure that polyurethane foam produced by the flame-retardant combined polyether has proper hardness and is consistent in hardness and softness; the melamine is used as a raw material to synthesize the polyether polyol A, and the diethyl aluminum hypophosphite is introduced into the synthesis of the polyether polyol C, so that the combined polyether structurally has a flame-retardant group, the integral stability of the combined polyether is ensured, the phenomenon that a flame retardant is separated from other components in the storage process is avoided, and the flame-retardant effect of producing and manufacturing the flame-retardant polyurethane is better; the combination technology of emulsification and micro-emulsification ensures that all components of the multi-component combined polyether are compatible with each other, and the obtained combined polyether has better uniformity and higher stability.
Detailed Description
The following examples are used to specifically illustrate a flame retardant type conjugate polyether and a preparation method thereof.
Example 1: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 325: 10: 160: 110: 230: 0.003: 0.0011, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, displacing air, heating to 130 ℃, slowly adding the propylene oxide, reacting for 40min under 0.5MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.10 MPa to obtain polyether polyol A with the hydroxyl value of 430 mgKOH/g;
(2) processing peanut shells into 100-mesh powder, then respectively weighing peanut shell powder, ethylene glycol and concentrated sulfuric acid according to the mass ratio of 100: 650: 20, uniformly mixing, heating to 150 ℃, treating for 75min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 140 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a bimetal hydride complex catalyst MMC with a hydroxyl value of 56mgKOH/g according to the mass ratio of 100: 320: 5: 0.003, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the bimetal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 125 ℃, vacuumizing to-0.097 MPa, dehydrating for 100min, closing the vacuum, slowly dropwise adding the propylene oxide, continuing to react for 75min after the dropwise addition is finished, and then vacuumizing at 80 ℃ to remove unreacted residual monomers to obtain polyether polyol C with the hydroxyl value of 30 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 420mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 35: 520;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 700mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 7.0;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 30min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 75 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsify for 75min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 2: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300: 8: 150: 100: 200: 0.001: 0.0007, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, displacing air, heating to 100 ℃, slowly adding the propylene oxide, reacting for 30min under 0.4MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09 MPa to obtain polyether polyol A with the hydroxyl value of 410 mgKOH/g;
(2) processing peanut shells into powder of 40 meshes, then respectively weighing peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 600: 15, uniformly mixing, heating to 140 ℃, treating for 60min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 110 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 52mgKOH/g according to a mass ratio of 100: 280: 3: 0.002, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120 ℃, vacuumizing to-0.095 MPa, dehydrating for 80min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 60min after dropwise adding is finished, and vacuumizing at 70 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 20 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 360mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 30: 480;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 600mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 6.5;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 20min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicon oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined solution;
(7) heating the multi-component combined solution to 60 ℃, then slowly adding the compound microemulsion while stirring, continuing stirring for microemulsifying for 60min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 3: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 350: 12: 170: 120: 260: 0.005: 0.0015, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 160 ℃, slowly adding the propylene oxide, reacting for 50min under 0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.11 MPa to obtain polyether polyol A with the hydroxyl value of 450 mgKOH/g;
(2) processing peanut shells into 160-mesh powder, then respectively weighing peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 700: 25, uniformly mixing, heating to 160 ℃, treating for 90min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 170 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 60mgKOH/g according to a mass ratio of 100: 360: 7: 0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 130 ℃, vacuumizing to-0.099 MPa, dehydrating for 120min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 90min after dropwise adding is finished, and vacuumizing at 90 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 40 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 480mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 40: 560;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 800mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 7.5;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 40min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 90 ℃, then slowly adding the compound microemulsion while stirring, continuing stirring and microemulsifying for 90min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 4: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300: 10: 170: 100: 230: 0.005: 0.0007, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, displacing air, heating to 130 ℃, slowly adding the propylene oxide, reacting for 30min under 0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.10 MPa to obtain polyether polyol A with the hydroxyl value of 450 mgKOH/g;
(2) processing peanut shells into powder of 40 meshes, then respectively weighing peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 650: 25, uniformly mixing, heating to 140 ℃, treating for 75min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 170 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 52mgKOH/g according to a mass ratio of 100: 280: 5: 0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 125 ℃, vacuumizing to-0.099 MPa, dehydrating for 80min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 75min after dropwise adding is finished, and vacuumizing at 90 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 20 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 480mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 30: 520;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 800mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 6.5;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 30min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 90 ℃, then slowly adding the compound microemulsion while stirring, continuing stirring for microemulsifying for 60min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 5: the flame-retardant combined polyether comprises the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 325: 12: 150: 110: 260: 0.001: 0.0011, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 160 ℃, slowly adding the propylene oxide, reacting for 40min under 0.4MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.11 MPa to obtain polyether polyol A with the hydroxyl value of 410 mgKOH/g;
(2) processing peanut shells into 100-mesh powder, then respectively weighing peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 700: 15, uniformly mixing, heating to 150 ℃, treating for 90min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 110 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 56mgKOH/g according to a mass ratio of 100: 320: 7: 0.002, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 130 ℃, vacuumizing to-0.095 MPa, dehydrating for 100min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 90min after dropwise adding is finished, and vacuumizing at 70 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 30 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 360mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 35: 560;
the silicone oil stabilizer is a silicone-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 600mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 7.0;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 40min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 60 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsify for 75min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 6: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 350: 8: 160: 120: 200: 0.003: 0.0015, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 100 ℃, slowly adding the propylene oxide, reacting for 50min under 0.5MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09 MPa to obtain polyether polyol A with the hydroxyl value of 430 mgKOH/g;
(2) processing peanut shells into 160-mesh powder, then respectively weighing peanut shell powder, ethylene glycol and concentrated sulfuric acid according to the mass ratio of 100: 600: 20, uniformly mixing, heating to 160 ℃, treating for 60min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 140 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 60mgKOH/g according to the mass ratio of 100: 360: 3: 0.003, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120 ℃, vacuumizing to-0.097 MPa, dehydrating for 120min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 60min after dropwise adding is finished, and vacuumizing at 80 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 40 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 420mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 40: 480;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 700mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 7.5;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 20min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multicomponent composite liquid to 75 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsion for 90min after the addition is finished, and cooling to room temperature to prepare the flame-retardant composite polyether.
Example 7: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300: 8: 150: 100: 200: 0.001: 0.0007, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, displacing air, heating to 100 ℃, slowly adding the propylene oxide, reacting for 30min under 0.4MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09 MPa to obtain polyether polyol A with the hydroxyl value of 410 mgKOH/g;
(2) processing peanut shells into 100-mesh powder, then respectively weighing peanut shell powder, ethylene glycol and concentrated sulfuric acid according to the mass ratio of 100: 650: 20, uniformly mixing, heating to 150 ℃, treating for 75min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 140 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double-metal hydride complex catalyst MMC with a hydroxyl value of 60mgKOH/g according to a mass ratio of 100: 360: 7: 0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double-metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 130 ℃, vacuumizing to-0.099 MPa, dehydrating for 120min, closing the vacuum, slowly dropwise adding propylene oxide, continuing to react for 90min after dropwise adding is finished, and vacuumizing at 90 ℃ to remove unreacted residual monomers to obtain polyether polyol C with a hydroxyl value of 40 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 360mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 35: 520;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 800mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 7.5;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 20min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 75 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsify for 75min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
Example 8: the flame-retardant combined polyether and the preparation method thereof comprise the following preparation processes:
(1) respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 310: 9: 159: 118: 220: 0.002: 0.0009, uniformly mixing the melamine, the N, N-dimethylacetamide, the ethyl acetate, the pyridine, the potassium tert-butoxide and the sodium hydroxide, adding the mixture into a reaction kettle, displacing air, heating to 150 ℃, slowly adding the propylene oxide, reacting for 35min under 0.45MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.095 MPa to obtain polyether polyol A with the hydroxyl value of 415 mgKOH/g;
(2) processing peanut shells into powder of 60 meshes, then respectively weighing peanut shell powder, ethylene glycol and concentrated sulfuric acid according to the mass ratio of 100: 660: 16, uniformly mixing, heating to 148 ℃, treating for 68min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B with the hydroxyl value of 118 mgKOH/g;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a bimetal hydride complex catalyst MMC with a hydroxyl value of 53mgKOH/g according to the mass ratio of 100: 285: 6: 0.0026, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the bimetal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 123 ℃, vacuumizing to-0.096 MPa, dehydrating for 86min, closing vacuum, slowly dropwise adding propylene oxide, continuing to react for 66min after dropwise adding is finished, and then vacuumizing at 76 ℃ to remove unreacted residual monomers to obtain polyether polyol C with the hydroxyl value of 28 mgKOH/g;
(4) weighing the following raw materials according to the formula:
the polyester polyol has a hydroxyl value of 380mgKOH/g, is aromatic polyester polyol and is obtained by polymerizing phthalic anhydride and dihydric alcohol;
the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 38: 488;
the silicone oil stabilizer is a silicon-carbon bond hydrolysis-resistant silicone foam stabilizer, the viscosity is 670mPa & s at 25 ℃, and the pH value (1% aqueous solution) is 6.7;
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 27min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 64 ℃, then slowly adding the compound microemulsion while stirring, continuing stirring for microemulsion for 66min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
The following tests prove the effect of the flame-retardant combined polyether in the embodiment 1 of the invention:
standing for 7 days, no layering, no color change, and uniform liquid phase.
The combined polyether and the isocyanate in the embodiment 1 are weighed according to the mass ratio of 100: 110 respectively, mixed and foamed, and the detection results are as follows:
milk white time: 3.2s, foaming time: 28s, expansion ratio: 182, no shrinkage, uniform cell size, oxygen index: 38.6 (%) and left flame self-extinguishing for 1.5s after ignition without dripping.
The test result shows that the polyurethane prepared in the embodiment 1 has good stability and processing technology performance, and has excellent flame retardance, no shrinkage, uniform and stable foam pores and good overall quality.
Claims (8)
1. The flame-retardant combined polyether is characterized by being prepared from the following raw materials in parts by weight:
2. the flame retardant polyether composition according to claim 1, wherein the polyether polyol A has a hydroxyl value of 410-450mgKOH/g, and is prepared by the following steps: respectively weighing melamine, propylene oxide, kieselguhr, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300-350: 8-12: 150-170: 100-200-260: 0.001-0.005: 0.0007-0.0015, uniformly mixing the melamine, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 100-160 ℃, slowly adding the propylene oxide, reacting for 30-50min under 0.4-0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the kieselguhr, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09-0.11 MPa in vacuum to obtain the polyether polyol A.
3. The flame retardant polyether composition according to claim 1, wherein the polyether polyol B has a hydroxyl value of 110-170mgKOH/g, and is prepared by the following steps: processing the peanut shell into powder of 40-160 meshes, then weighing the peanut shell powder, glycol and concentrated sulfuric acid respectively according to the mass ratio of 100: 600-700: 15-25, uniformly mixing, heating to 140-160 ℃, treating for 60-90min, cooling with cold water to stop the reaction, and separating to obtain polyether polyol B.
4. The flame-retardant conjugate polyether according to claim 1, wherein the polyether polyol C has a hydroxyl value of 20 to 40mgKOH/g, and is prepared by the process comprising: weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double metal hydride complex catalyst MMC with a hydroxyl value of 52-60mgKOH/g according to the mass ratio of 100: 280 plus 360: 3-7: 0.002-0.004 respectively, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120 plus 130 ℃, vacuumizing to-0.095 MPa-0.099 MPa, dehydrating for 80-120min, closing the vacuum, slowly dripping propylene oxide, continuing to react for 60-90min after dripping is finished, vacuumizing at 70-90 ℃ to remove unreacted residual monomers to obtain polyether polyol C.
5. The flame retardant type composite polyether according to claim 1, wherein said polyester polyol has a hydroxyl value of 360-480mgKOH/g, is an aromatic polyester polyol, and is obtained by polymerizing phthalic anhydride and a diol.
6. The flame-retardant combined polyether according to claim 1, wherein the compound microemulsion is prepared by compounding C8-C9 alkylphenol ethoxylate, fatty alcohol polyoxyethylene ether AEO-3 and dioctadecyldimethylammonium chloride according to the mass ratio of 100: 30-40: 480-560.
7. The flame-retardant conjugate polyether according to claim 1, wherein the silicone oil stabilizer is a silicone cell stabilizer with a silicon-carbon bond hydrolysis resistance type, and has a viscosity of 600-800mPa s at 25 ℃ and a pH (1% aqueous solution) of 6.5-7.5.
8. The preparation method of the flame-retardant combined polyether according to claim 1, wherein the preparation process comprises the following steps:
(1) respectively weighing melamine, propylene oxide, diatomite, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide according to the mass ratio of 100: 300-350: 8-12: 150-170: 120: 200-260: 0.001-0.005: 0.0007-0.0015, uniformly mixing the melamine, N-dimethylacetamide, ethyl acetate, pyridine, potassium tert-butoxide and sodium hydroxide, adding the mixture into a reaction kettle, replacing air, heating to 100-160 ℃, slowly adding the propylene oxide, reacting for 30-50min under 0.4-0.6MPa, cooling, adjusting the liquid in the reaction kettle to be neutral, adding the diatomite, uniformly mixing, filtering and desalting, and removing the solvent from the filtrate under-0.09-0.11 MPa to obtain polyether polyol A;
(2) processing the peanut shell into powder of 40-160 meshes, then respectively weighing the peanut shell powder, glycol and concentrated sulfuric acid according to the mass ratio of 100: 600-700: 15-25, uniformly mixing, heating to 140-160 ℃, treating for 60-90min, cooling with cold water to terminate the reaction, and separating to obtain polyether polyol B;
(3) respectively weighing primary polyether polyol, propylene oxide, diethyl aluminum hypophosphite and a double metal hydride complex catalyst MMC with a hydroxyl value of 52-60mgKOH/g according to the mass ratio of 100: 280 plus 360: 3-7: 0.002-0.004, putting the primary polyether polyol, the diethyl aluminum hypophosphite and the double metal hydride complex catalyst MMC into a reaction kettle, replacing air, heating to 120 plus 130 ℃, vacuumizing to-0.095-0.099 MPa, dehydrating for 80-120min, closing vacuum, slowly dripping propylene oxide, continuing to react for 60-90min after dripping is finished, vacuumizing at 70-90 ℃, and removing unreacted residual monomers to obtain polyether polyol C;
(4) weighing the following raw materials according to the formula:
(5) uniformly mixing polyether polyol A, polyether polyol B, polyether polyol C, polyester polyol and Tween 80, and carrying out emulsification treatment for 20-40min to obtain a polyol mixture;
(6) uniformly mixing a polyol mixture, A-33, stannous octoate, a silicone oil stabilizer, deionized water and cyclopentane to obtain a multi-component combined liquid;
(7) heating the multi-component combined solution to 60-90 ℃, then slowly adding the compound microemulsion while stirring, continuing to stir and microemulsify for 60-90min after the addition is finished, and cooling to room temperature to prepare the flame-retardant combined polyether.
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