CN116948163B - Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof - Google Patents
Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof Download PDFInfo
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- CN116948163B CN116948163B CN202311210813.9A CN202311210813A CN116948163B CN 116948163 B CN116948163 B CN 116948163B CN 202311210813 A CN202311210813 A CN 202311210813A CN 116948163 B CN116948163 B CN 116948163B
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- halogen
- polyether polyol
- free flame
- dopo
- dihydroxydopo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 81
- 229920000570 polyether Polymers 0.000 title claims abstract description 81
- 229920005862 polyol Polymers 0.000 title claims abstract description 78
- 150000003077 polyols Chemical class 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 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 62
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004917 polyol method Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 230000005587 bubbling Effects 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 7
- 239000011496 polyurethane foam Substances 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 7
- 239000004814 polyurethane Substances 0.000 abstract description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920002614 Polyether block amide Polymers 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- -1 isocyanate siloxane Chemical class 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000004526 silane-modified polyether Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of polyether polyol, and particularly relates to dihydroxyDOPO halogen-free flame-retardant polyether polyol, and a preparation method and application thereof. The dihydroxy DOPO halogen-free flame-retardant polyether polyol is obtained by polymerizing dihydroxy DOPO and polyol serving as a mixed initiator with alkylene oxide under the action of a composite catalyst, wherein the dihydroxy DOPO accounts for 35-62% of the mixed initiator in percentage by mass. The dihydroxyl DOPO halogen-free flame-retardant polyether polyol prepared by the invention has better mechanical strength, activity and flame-retardant property compared with other polyether polyols when being used for polyurethane materials by introducing a ternary phenanthrene ring structure in DOPO.
Description
Technical Field
The invention belongs to the technical field of polyether polyol, and particularly relates to dihydroxyDOPO halogen-free flame-retardant polyether polyol, and a preparation method and application thereof.
Background
The rigid foam polyether polyol is a main upstream raw material of the current polyurethane heat-insulation product, is a polyether polyol with enough crosslinking degree and rigidity, high functionality, high hydroxyl value and lower molecular weight, and has the functionality of 3-8 and the hydroxyl value of 300-700 mgKOH/g. The rigid foam polyether polyol reacts with polyisocyanate after mixing a foaming agent and a catalyst to form foam with a crosslinked network structure, and the formed foam product has high hardness, high compressive strength, good dimensional stability and good temperature resistance, and is commonly used in the fields of household electrical appliance heat insulation, industrial heat preservation, building energy conservation and the like. Polyether polyols of different compound structures are used for rigid polyurethane foam and can obtain various service properties.
For example, patent CN113698905a discloses a DOPO-containing flame retardant silane modified polyether sealant and a preparation method thereof, wherein polyether with two hydroxyl ends is reacted with isocyanate siloxane to obtain an MS glue base polymer; reacting amino-terminated polysiloxane with m-hydroxybenzaldehyde, then reacting the product with DOPO, removing the solvent in the reaction system under reduced pressure, and reacting with isocyanate siloxane to obtain an organosilicon flame retardant additive with two ends of alkoxy end-capped and DOPO groups; under the protection of nitrogen, the MS rubber base polymer, the organic silicon flame retardant additive, the filler and the catalyst are vacuumized and mixed in a star-shaped mixer according to the proportion, and are filled. According to the invention, the organic silicon flame retardant additive with two ends of the alkoxy end capped and DOPO groups is added into the MS sealant, the additive participates in the curing reaction of the MS sealant, and can not be separated out from the MS sealant, and the content of the organic silicon chain segments in the MS sealant is improved, so that the flame retardant effect of the MS sealant can be obviously improved.
Patent CN112745500A discloses a DOPO-based reaction type flame retardant modified polyether amide and a preparation method thereof, wherein caprolactam is melted and then added into a reaction vessel together with dibasic acid and a ring-opening agent, and ring-opening reaction is carried out under stirring to obtain an oligomer; adding DOPO-based reactive flame retardant into a reaction container, and carrying out esterification reaction under stirring to obtain polyamide prepolymer; adding polyglycol and polycondensation catalyst into the reaction container, and stirring to perform polycondensation to obtain the flame retardant polyether amide. According to the invention, the DOPO-based reactive flame retardant takes hydroxyl groups as active groups at two ends, and participates in the copolymerization of polyether amide, so that the flame retardant property of the polyether amide is effectively improved.
As described above, DOPO modified polyol with different compound structures and preparation methods can be used for preparing polyurethane materials with different forms to obtain different service performances. However, the synthesis of DOPO modified polyol in the prior art is either harsh or complicated in steps, and is difficult to prepare industrially on a large scale at low cost. The development process is simple, the energy consumption is lower, the popularization and the use of DOPO modified polyol are facilitated, and the additional value of DOPO is better improved. In addition, raw materials used in the production of the rigid polyurethane foam are all taken from petroleum resources, and the development and the utilization of the petroleum resources are also subject to price, resource and environmental protection pressure.
Disclosure of Invention
The purpose of the invention is that: the invention provides a dihydroxy DOPO halogen-free flame-retardant polyether polyol, which has the advantages of good flame retardant property, high mechanical strength and environmental protection when being used for preparing polyurethane materials.
The dihydroxyl DOPO halogen-free flame-retardant polyether polyol is prepared by polymerizing dihydroxyl DOPO and polyol serving as mixed initiators with alkylene oxide under the action of a composite catalyst.
In the invention, the polyalcohol is one or more of sucrose, 1, 4-butanediol, diethanolamine, diethylene glycol, octanediol, hexanediol and trimethylolethane.
In the invention, the dihydroxyl DOPO accounts for 35-62% of the mass of the mixed initiator.
The structure of the dihydroxydopo is as follows:
。
the dihydroxyl DOPO has a molecular structure containing a biphenyl ring and a phenanthrene ring structure, and particularly, a side phosphorus group is introduced in a mode of cyclic O=P-O bond, so that the dihydroxyl DOPO has higher thermal stability and chemical stability than the common acyclic organic phosphate, has better flame retardant property and has higher compression strength of the prepared polyurethane rigid foam. The dihydroxy DOPO is used as a reactive flame retardant and an additive flame retardant, and the synthesized polyether polyol has the advantages of no halogen, no smoke, no toxicity and lasting flame retardant property. When the content of the dihydroxyDOPO is lower than 20%, the better flame retardant property cannot be achieved; when the dihydroxydopo is too high (more than 62%), stirring is impossible because the dihydroxydopo is a solid, and normal production is impossible.
In the invention, the composite catalyst is a mixture of a catalyst A and a catalyst B; the catalyst A is one or more of KOH, dimethylacetamide (DMA) and potassium methoxide; the catalyst B is one or more of triethylamine, N-dimethylbenzylamine and dimethylcyclohexylamine. The catalyst B has high catalytic activity in the early reaction stage, but the catalytic activity in the late reaction stage is reduced, and even the catalytic activity is lost along with the normal reaction time, so the invention adopts two catalysts for compounding to improve the catalytic activity of the whole reaction process, thereby shortening the production period.
Preferably, the addition amount of the composite catalyst is 0.5-1.2% of the total mass of the mixed initiator and the alkylene oxide.
Preferably, the mass ratio of the catalyst A to the catalyst B is (0.2-0.8): 1.
In the present invention, the alkylene oxide is one or both of propylene oxide and ethylene oxide.
Preferably, the mass ratio of the alkylene oxide to the mixed initiator is (0.7-1.4): 1.
The preparation method of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol comprises the following steps:
(1) Adding dihydroxyDOPO, polyol and a composite catalyst into a reaction kettle, dropwise adding part of alkylene oxide to carry out polyether chain extension at the temperature of 85-95 ℃ and the vacuum degree of-0.08 to-0.1 MPa, and continuing internal pressure reaction for 1-2 h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And heating the intermediate of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol to 115-125 ℃, dropwise adding the rest of alkylene oxide for end-capping synthesis, and continuing the internal pressure reaction for 2-3 hours after the feeding is finished to obtain a dihydroxyl DOPO halogen-free flame-retardant polyether polyol crude polymer, and removing the rest of micromolecules by nitrogen bubbling to obtain the dihydroxyl DOPO halogen-free flame-retardant polyether polyol.
In the step (1), the addition amount of the alkylene oxide is 63-71% of the total mass of the alkylene oxide.
In the step (2), nitrogen is filled in the reaction kettle to be pressurized to 0.2-0.3 MPa during nitrogen bubbling, and the crude polymer of the dihydroxyDOPO halogen-free flame-retardant polyether polyol is cooled to 95-105 ℃.
The invention firstly makes the mixed initiator and the alkylene oxide carry out polymerization reaction at relatively low temperature, and then heats up to relatively high temperature to carry out reaction, because the activity of the micromolecular alcohol is high at high temperature, the reaction is firstly carried out at low temperature to help the full reaction of the dihydroxyl DOPO and the alkylene oxide, and the residual of the dihydroxyl DOPO is avoided.
Specifically, the preparation method of the dihydroxyl DOPO halogen-free flame-retardant polyether comprises the following steps:
(1) Adding dihydroxyDOPO, polyol and a composite catalyst into a reaction kettle, stamping for 20min under 0.25MPa, heating to 85-95 ℃ under the vacuum-pumping negative pressure atmosphere, vacuumizing to-0.08 to-0.1 MPa, dropwise adding alkylene oxide for polyether chain extension, and continuing the internal pressure reaction for 1-2 h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And heating the intermediate of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol to 115-125 ℃, dropwise adding alkylene oxide for end-capping synthesis, continuing to perform internal pressure reaction for 2-3 h after feeding to obtain a dihydroxyl DOPO halogen-free flame-retardant polyether polyol crude polymer, charging nitrogen, pressurizing to 0.2-0.3 MPa, enabling the pressure not to be reduced, cooling the dihydroxyl DOPO halogen-free flame-retardant polyether polyol crude polymer to 95-105 ℃, performing nitrogen bubbling to remove residual small molecules, cooling to 75-80 ℃ after bubbling for 1-2 h, and discharging to obtain the dihydroxyl DOPO halogen-free flame-retardant polyether polyol.
The application of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol disclosed by the invention is used for preparing rigid polyurethane foam.
Compared with the prior art, the invention has the beneficial effects that:
(1) The dihydroxyl DOPO adopted by the invention is prepared from natural resin, can be used as a regenerated green environment-friendly material to replace petrochemical products, and has the advantages of low cost and good environment friendliness when being used for preparing polyurethane materials;
(2) The dihydroxy DOPO halogen-free flame-retardant polyether polyol prepared by the invention has better mechanical strength, activity and flame-retardant property compared with other polyether polyols when being used for polyurethane materials by introducing a ternary phenanthrene ring structure in the dihydroxy DOPO.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples. All materials used in the examples are commercially available, except as specified.
Example 1
The preparation method comprises the following steps of:
(1) Adding 500g of dihydroxyDOPO, 150g of sucrose, 115g of diethanolamine, 20g of diethylene glycol, 40g of trimethylolethane, 5g of KOH and 9g of triethylamine into a reaction kettle, stamping for 20min under 0.25MPa, heating to 90 ℃ under vacuum negative pressure, vacuumizing to-0.09 MPa, dropwise adding 450g of ethylene oxide for polyether chain extension, and continuing internal pressure reaction for 2h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And (3) heating the intermediate of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol to 120 ℃, continuously dropwise adding 187g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 2h, pressurizing to 0.25MPa by filling nitrogen, reducing the pressure in the kettle to 100 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, reducing the temperature to 80 ℃ after bubbling for 2h, and discharging to obtain the dihydroxyl DOPO halogen-free flame-retardant polyether polyol.
Example 2
The preparation method comprises the following steps of:
(1) 365g of dihydroxyDOPO, 180g of sucrose, 85g of diethanolamine, 20g of diethylene glycol, 40g of hexanediol, 4g of DMA and 5g of N, N-dimethylbenzylamine are added into a reaction kettle, the mixture is punched at 0.25MPa for 20min, the temperature is raised to 95 ℃ under the vacuum negative pressure atmosphere, the mixture is vacuumized to-0.08 MPa, 580g of ethylene oxide is dropwise added for polyether chain extension, and internal pressure reaction is continued for 1h after the feeding is completed, so that the dihydroxyDOPO halogen-free flame retardant polyether polyol intermediate is obtained;
(2) And (3) heating the intermediate of the dihydroxyDOPO halogen-free flame-retardant polyether polyol to 115 ℃, continuously dropwise adding 335g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 3 hours, charging nitrogen and pressurizing to 0.2MPa, wherein the pressure in the kettle is not reduced any more, cooling to 95 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling to 80 ℃ after bubbling for 1 hour, and discharging to obtain the dihydroxyDOPO halogen-free flame-retardant polyether polyol.
Example 3
The preparation method comprises the following steps of:
(1) Adding 315g of dihydroxyDOPO, 205g of sucrose, 55g of diethanolamine, 49g of octylglycol, 2g of potassium methoxide, 5g of N, N-dimethylbenzylamine and 5g of dimethylcyclohexylamine into a reaction kettle, stamping for 20min under 0.25MPa, heating to 85 ℃ under a vacuum negative pressure atmosphere, vacuumizing to-0.1 MPa, dropwise adding 316g of ethylene oxide for polyether chain extension, and continuing an internal pressure reaction for 1.5h after feeding to obtain a dihydroxyDOPO halogen-free flame retardant polyether polyol intermediate;
(2) And (3) heating the intermediate of the dihydroxyDOPO halogen-free flame-retardant polyether polyol to 125 ℃, continuously dropwise adding 139g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 2.5h, charging nitrogen, pressurizing to 0.3MPa, and keeping the pressure in the kettle from decreasing, cooling to 105 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling to 80 ℃ after bubbling for 1h, and discharging to obtain the dihydroxyDOPO halogen-free flame-retardant polyether polyol.
Example 4
The preparation method comprises the following steps of:
(1) Adding 210g of dihydroxyDOPO, 220g of sucrose, 14g of solid sorbitol, 66g of diethanolamine, 23g of 1, 4-butanediol, 4g of KOH, 3g of N, N-dimethylbenzylamine and 4g of dimethylcyclohexylamine into a reaction kettle, stamping for 20min under the condition of 0.25MPa leakage test, heating to 90 ℃ under the vacuum negative pressure, vacuumizing to-0.09 MPa, dropwise adding 330g of ethylene oxide for polyether chain extension, and continuing internal pressure reaction for 2h after feeding to obtain a dihydroxyDOPO halogen-free flame retardant polyether polyol intermediate;
(2) And (3) heating the intermediate of the dihydroxyDOPO halogen-free flame-retardant polyether polyol to 120 ℃, continuously dropwise adding 192g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 2h, pressurizing to 0.25MPa by filling nitrogen, reducing the pressure in the kettle to 100 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, reducing the temperature to 80 ℃ after bubbling for 2h, and discharging to obtain the dihydroxyDOPO halogen-free flame-retardant polyether polyol.
Comparative example 1
The polyether polyol is prepared according to the following steps:
330g of sucrose, 55g of solid sorbitol, 75g of diethylene glycol, 246g of palm oil and 10g of fatty amine catalyst are added into a reaction kettle, the mixture is punched for 20min under the condition of 0.25MPa leakage test, the temperature is raised to 105 ℃ under the vacuum negative pressure atmosphere, meanwhile, the pressure of nitrogen atmosphere in the kettle is kept at 0.13+/-0.02 MPa, 921g of propylene oxide is dropwise added, after the propylene oxide is dropwise added, the heat preservation reaction is continued for 3h until the pressure in the kettle is not reduced, the temperature is reduced to 100 ℃, nitrogen bubbling is carried out, residual micromolecular substances in the product are removed, the temperature is reduced to 80 ℃ after the bubbling is carried out for 2h, and the polyether polyol is obtained after discharging.
Comparative example 2
The polyether polyol is prepared according to the following steps:
adding 335g of sucrose, 170g of diethylene glycol and 11g of chromium acetylacetonate catalyst into a reaction kettle, stamping for 20min under the condition of 0.25MPa leakage test, heating to 105 ℃ under the vacuum negative pressure atmosphere, simultaneously keeping the nitrogen atmosphere pressure in the kettle at 0.13+/-0.02 MPa, dropwise adding 955g of propylene oxide, continuing to carry out heat preservation reaction for 3h after the propylene oxide is dropwise added until the pressure in the kettle is not reduced, cooling to 100 ℃, carrying out nitrogen bubbling, removing residual micromolecular substances in the product, cooling to 80 ℃ after 2h of bubbling, and discharging to obtain the polyether polyol.
Comparative example 3
The preparation method comprises the following steps of:
(1) Adding 500g of dihydroxyDOPO, 150g of sucrose, 115g of diethanolamine, 20g of diethylene glycol, 40g of trimethylolethane, 5g of KOH and 9g of triethylamine into a reaction kettle, stamping for 20min under the condition of 0.25MPa leakage test, heating to 120 ℃ under the vacuum negative pressure atmosphere, vacuumizing to-0.09 MPa, dropwise adding 450g of ethylene oxide for polyether chain extension, and continuing internal pressure reaction for 2h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And (3) heating the intermediate of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol to 120 ℃, continuously dropwise adding 187g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 2h, pressurizing to 0.25MPa by filling nitrogen, reducing the pressure in the kettle to 100 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, reducing the temperature to 80 ℃ after bubbling for 2h, and discharging to obtain the dihydroxyl DOPO halogen-free flame-retardant polyether polyol.
Comparative example 4
The preparation method comprises the following steps of:
(1) Adding 500g of dihydroxyDOPO, 150g of sucrose, 115g of diethanolamine, 20g of diethylene glycol, 40g of trimethylolethane, 5g of KOH and 9g of triethylamine into a reaction kettle, stamping for 20min under 0.25MPa, heating to 90 ℃ under vacuum negative pressure, vacuumizing to-0.09 MPa, dropwise adding 450g of ethylene oxide for polyether chain extension, and continuing internal pressure reaction for 2h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And (3) heating the intermediate of the dihydroxyDOPO halogen-free flame-retardant polyether polyol to 90 ℃, continuously dropwise adding 187g of propylene oxide for end-capping synthesis, preserving heat after feeding, continuously carrying out internal pressure reaction for 2h, pressurizing to 0.25MPa by filling nitrogen without reducing the pressure in the kettle, heating to 100 ℃, carrying out nitrogen bubbling, removing residual micromolecule substances in the product, cooling to 80 ℃ after bubbling for 2h, and discharging to obtain the dihydroxyDOPO halogen-free flame-retardant polyether polyol.
The polyether polyols obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to performance tests according to the following criteria, wherein the hydroxyl number was tested with reference to the standard GB/T12008.3-1989 and the viscosity was tested with reference to the standard GB/T12008.7-2010. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the reaction temperatures of step (1) and step (2) of comparative example 3 are 120℃and since the reactivity of the solid initiator and the liquid initiator differ greatly at high reaction temperatures, a high reaction temperature of step (1) results in incomplete reaction of the solid initiator and a decrease in the functionality and hydroxyl number of the final polyether polyol. Comparative example 4 the reaction temperatures of step (1) and step (2) were 90 ℃ and the reactivity of the mixed starter was lower at low reaction temperatures, which resulted in longer production cycles of the final polyether polyol on the one hand and in a higher content of small molecules of the polyether polyol formed and a lower viscosity on the other hand.
The polyether polyols obtained in examples 1-4 and comparative examples 1-2 were compounded according to the raw material composition of Table 2 to obtain a material A, wherein MAYCATPC8 of Jiangsu Mei Si chemical Co., ltd., a flame retardant was tris (2-chloroethyl) phosphate (TCEP), and a physical foaming agent was 141b; the material B is PM200 of Wanhua chemical group Co., ltd. And (3) mixing the materials A and B according to the NCO index of 1.04, uniformly mixing, and foaming to obtain a polyurethane foam sample. The amounts of the raw materials in Table 2 are in parts by mass.
TABLE 2
The polyurethane foam samples obtained were subjected to performance tests, wherein the strength was tested according to the standard GB/T8813-2020, the oxygen index was tested according to the standard GB/T2918-1988, and the activity was determined as the time taken from the start of mixing the materials A and B to the start of wire drawing, and the shorter the time, the higher the activity was proved. The test results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the rigid polyurethane foam prepared from the polyether polyol of the invention has obviously improved flame retardant property, strength and activity.
Claims (7)
1. A dihydroxy DOPO halogen-free flame retardant polyether polyol, characterized in that: the preparation method comprises the steps of adopting dihydroxyDOPO and polyalcohol as mixed initiators, and polymerizing the dihydroxyDOPO and polyalcohol with alkylene oxide under the action of a composite catalyst to obtain the catalyst;
the polyalcohol is one or more of sucrose, 1, 4-butanediol, diethanolamine, diethylene glycol, octanediol, hexanediol and trimethylolethane;
the structure of the dihydroxyDOPO is as follows:
;
the dihydroxyl DOPO accounts for 35-62% of the mixed initiator by mass;
the composite catalyst is a mixture of a catalyst A and a catalyst B; the catalyst A is one or more of KOH, dimethylacetamide and potassium methoxide; the catalyst B is one or more of triethylamine, N-dimethylbenzylamine and dimethylcyclohexylamine;
the preparation method of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol comprises the following steps:
(1) Adding dihydroxyDOPO, polyol and a composite catalyst into a reaction kettle, dropwise adding part of alkylene oxide to carry out polyether chain extension at the temperature of 85-95 ℃ and the vacuum degree of-0.08 to-0.1 MPa, and continuing internal pressure reaction for 1-2 h after feeding to obtain a dihydroxyDOPO halogen-free flame-retardant polyether polyol intermediate;
(2) And heating the intermediate of the dihydroxyl DOPO halogen-free flame-retardant polyether polyol to 115-125 ℃, dropwise adding the rest of alkylene oxide for end-capping synthesis, and continuing the internal pressure reaction for 2-3 hours after the feeding is finished to obtain a dihydroxyl DOPO halogen-free flame-retardant polyether polyol crude polymer, and removing the rest of micromolecules by nitrogen bubbling to obtain the dihydroxyl DOPO halogen-free flame-retardant polyether polyol.
2. The dihydroxydopo halogen-free flame retardant polyether polyol of claim 1 wherein: the mass ratio of the catalyst A to the catalyst B is (0.2-0.8): 1.
3. The dihydroxydopo halogen-free flame retardant polyether polyol of claim 1 wherein: the addition amount of the composite catalyst is 0.5-1.2% of the total mass of the mixed initiator and the alkylene oxide.
4. The dihydroxydopo halogen-free flame retardant polyether polyol of claim 1 wherein: the alkylene oxide is one or two of propylene oxide and ethylene oxide.
5. The dihydroxydopo halogen-free flame retardant polyether polyol of claim 1 wherein: the mass ratio of the alkylene oxide to the mixed initiator is (0.7-1.4): 1.
6. The dihydroxydopo halogen-free flame retardant polyether polyol of claim 1 wherein: in the step (1), the addition amount of the alkylene oxide is 63-71% of the total mass of the alkylene oxide.
7. Use of a dihydroxydopo halogen-free flame retardant polyether polyol according to any one of claims 1 to 5, wherein: for the preparation of rigid polyurethane foams.
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