CN115433226A - Phosphorus-containing polyol flame retardant and preparation method thereof - Google Patents
Phosphorus-containing polyol flame retardant and preparation method thereof Download PDFInfo
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- CN115433226A CN115433226A CN202211295266.4A CN202211295266A CN115433226A CN 115433226 A CN115433226 A CN 115433226A CN 202211295266 A CN202211295266 A CN 202211295266A CN 115433226 A CN115433226 A CN 115433226A
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- phosphorus
- containing polyol
- epoxidized
- flame retardant
- oil
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- 229920005862 polyol Polymers 0.000 title claims abstract description 55
- 150000003077 polyols Chemical class 0.000 title claims abstract description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 46
- 239000011574 phosphorus Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003063 flame retardant Substances 0.000 title abstract description 64
- 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 abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 14
- 239000008158 vegetable oil Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- -1 1-dimethyloxirane Chemical compound 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 24
- 239000011496 polyurethane foam Substances 0.000 abstract description 24
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000006260 foam Substances 0.000 description 17
- 239000004814 polyurethane Substances 0.000 description 15
- 229920002635 polyurethane Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 101100299648 Caenorhabditis elegans puf-5 gene Proteins 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000486761 Chilobrachys Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 244000262613 Michelia alba Species 0.000 description 1
- 235000003415 Michelia alba Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a phosphorus-containing polyol flame retardant and a preparation method thereof 1 is-H, -CH 3 ，‑C 2 H 5 -any one of Ph, R 2 Is epoxidized vegetable oil, aliphatic alkoxy, halogenated aliphatic alkoxy, n 1 、n 2 、n 3 、n 4 Are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 Less than or equal to 12. The phosphorus-containing polyol provided by the invention has the advantages of high quality, good color, controllable phosphorus content and low acid value, and for polyurethane foam, the phosphorus-containing polyol has good compatibility, can provide flame retardant property and can enhance the mechanical property of the polyurethane foam. The preparation method of the phosphorus-containing polyol flame retardant has moderate reaction temperature and does not use catalystThe catalyst has no by-product, and the excessive epoxy compound (micromolecule) after the reaction can be recycled, so that the atom economy is embodied, and the requirement of green chemistry is met.
Description
Technical Field
The invention belongs to the field of synthesis of flame retardants, and particularly relates to a novel phosphorus-containing polyol flame retardant and a preparation method thereof.
Background
Polyurethane (PU) refers to a polymer having repeating urethane groups (-NHCOO-) in the polymer backbone structure. PU is formed by polyaddition of polyester or polyether polyol with polyisocyanate in the presence of a catalyst, is highly appreciated by academia and industry due to its excellent performance, is considered as the "fifth most common plastic" following polyethylene, polyvinyl chloride, polypropylene and polystyrene, and is now widely used in the fields of leather processing, textiles, building materials, coatings, medicine, automobiles, defense, aerospace, and the like. However, because PU is a combustible or inflammable material, high concentrations of HCN, CO and NO are released during combustion 2 And toxic gases and smoke are generated, which not only is a serious potential safety hazard, but also threatens the lives, properties and safety of people all the time. It is therefore important to improve the heat resistance and flame retardancy of polyurethane materials.
At present, methods for improving the flame retardant property of polyurethane include additive flame retardants and the use of flame retardant polyether polyols. The halogen-containing flame retardant is gradually eliminated because the halogen-containing flame retardant generates a large amount of toxic gases such as hydrogen halide, dioxin and the like during combustion; the additive phosphate flame retardants such as triethyl phosphate, triphenyl phosphate, dimethyl methyl phosphate and the like have small molecular weight, and are easy to migrate in the foam along with the extension of time, so that the flame retardant property of the foam is reduced, and the mechanical property of the material is influenced; the flame-retardant polyether polyol can cause the formaldehyde content of polyurethane foam to seriously exceed the standard. The traditional additive flame retardant in a physical blending mode has the defects of easy occurrence of flame retardant precipitation, migration and the like in the use process of a polyurethane product.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of the existing flame retardant, the invention provides a novel phosphorus-containing polyol flame retardant to solve the problems of easy precipitation, poor compatibility with materials, partial hydrolysis and the like of an additive phosphate flame retardant. The novel flame retardant provided by the invention contains hydroxyl functional groups, so that the novel flame retardant can react with high-molecular monomers such as isocyanate and the like, when polyurethane is synthesized, the phosphorus-containing polyol flame retardant is added as a raw material, and the flame-retardant unit is inserted into a main chain or a side chain of the polyurethane in an embedding, crosslinking and other modes, so that the polyurethane is permanently flame-retardant, and the defects that the additive flame retardant is easy to separate out and migrate and the like are effectively overcome.
The invention also provides a preparation method of the novel phosphorus-containing polyol flame retardant.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a phosphorus-containing polyol having the following structural formula:
wherein R is 1 is-H, -CH 3 ，-C 2 H 5 -any one of Ph, R 2 Is an epoxidized vegetable oil, an aliphatic alkoxy radical or a halogenated aliphatic alkoxy radical, n 1 、n 2 、n 3 、n 4 Are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 ≤12(n 1 、n 2 、n 3 、n 4 Is R 2 Number of substituents)
Preferably, when R is 2 When it is an aliphatic alkoxy group or a halogenated aliphatic alkoxy group, n 1 、n 2 、n 3 、n 4 Are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 12 or less, wherein the aliphatic alkoxy or halogenated aliphatic alkoxy is any one of the following groups:
said R is 2 In the case of epoxidized vegetable oils, n 1 、n 2 、n 3 、n 4 1, and the epoxidized vegetable oil is any one of the following:
epoxidized soybean oil, epoxidized castor oil, epoxidized corn oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized tung oil, ring (C)Oxy soybean oil methyl ester. When R is 2 In the case of epoxidized vegetable oil, since the epoxidized vegetable oil has a relatively high molecular weight, contains 3 carbon chains per molecule, 17 or 18 carbons per carbon chain, and may have only 1 epoxy group per carbon chain, it is less likely to undergo polymerization, so n is a major factor 1 、n 2 、n 3 、n 4 Are all 1.
Preferably, an organic solvent can be added when the epoxy vegetable oil is added, the viscosity of reactants can be reduced by using the organic solvent, the reaction is uniform, the yield is improved, and a product with low viscosity can be prepared without using the solvent and has no influence on the yield basically.
Still further, the solvent is 1, 4-dioxane, isopropanol, tert-butanol, toluene, ethyl acetate, tetrahydrofuran. After the reaction, the excess solvent was distilled off under reduced pressure to obtain a phosphorus-containing polyol.
Preferably, the phosphorus-containing polyol has a structural formula shown in any one of the following formulas:
the preparation method of the phosphorus-containing polyol comprises the following steps: adding polybasic phosphonic acid into a reaction device, then dropwise adding an epoxy compound, and after the epoxy compound is added, starting heat preservation reaction at the reaction temperature of 55-95 ℃ for 3-9h; when the epoxy compound is epoxy vegetable oil, organic solvent is required to be added, so that the viscosity is reduced, and the reaction rate is increased.
Wherein the polyphosphonic acid is hydroxyethylidene diphosphonic acid.
Wherein the epoxy compound is any one or more of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, 1-dimethyl ethylene oxide, glycidol and epoxidized vegetable oil.
Wherein the molar ratio of the polyphosphonic acid to the epoxy compound is 1: (4 to 14).
Wherein the solvent is any one or more of 1, 4-dioxane, isopropanol, tert-butanol, toluene, ethyl acetate and tetrahydrofuran.
Wherein, the reaction device is a normal pressure reaction device or a high pressure reaction device, if the high pressure reaction device is adopted, nitrogen is filled until the pressure in the kettle is 0.2-1MPa.
Further, the excess epoxy compound (small molecule) is recovered after the reaction to obtain the reactive phosphorus-containing polyol with an acid value of less than 2mg KOH/g and a hydroxyl value of 150-420mg KOH/g.
The phosphorus-containing polyol is used as a flame retardant in the preparation of high-flame-retardant polyurethane foam plastics.
The invention takes the hydroxy ethylidene diphosphonic acid which is a common scale treating agent as a raw material to design and synthesize the phosphorus-containing polyol, the polyol can be used as a reaction type flame retardant for flame retardance of polyurethane, and the defect that an additive type flame retardant is easy to migrate is overcome.
The invention designs phosphorus-containing polyol with a brand-new structure, the raw materials of the phosphorus-containing polyol mainly comprise hydroxyethylidene diphosphonic acid, the phosphorus-containing polyol is novel in structure and good in thermal stability, the decomposition temperature of the phosphorus-containing polyol is matched with that of polyurethane, the phosphorus-containing polyol is suitable for serving as a flame retardant of polyurethane foam, meanwhile, the synthesis method of the phosphorus-containing polyol is simple and efficient, and the product has a specific hydroxyl value and functionality. The flame retardant prepared by the method is gradually added when the rigid polyurethane foam is prepared, the flame retardant is added, so that the flame retardant effect is effectively improved, and meanwhile, the addition of a certain amount of flame retardant does not influence the mechanical property but has a certain promotion effect.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) The phosphorus-containing polyol provided by the invention has the following advantages: high quality, good color, controllable phosphorus content and low acid value, and not only has good compatibility with polyurethane foam, but also can provide flame retardant property and enhance the mechanical property of the polyurethane foam.
(2) The phosphorus-containing polyol prepared by the invention can realize better flame retardant property and can improve mechanical strength at the same time.
(2) The invention provides a synthesis method of a phosphorus-containing polyol flame retardant with a low acid value, the reaction temperature is moderate, no catalyst is used, no by-product is generated, and the excessive epoxy compound (micromolecule) after the reaction can be recycled, so that the atom economy is embodied, and the requirements of green chemistry are met.
Drawings
FIG. 1 is an appearance of a product, wherein (a) is the product of example 1 and (b) is the product of example 6;
FIG. 2 is a nuclear magnetic hydrogen spectrum of hydroxyethylidene diphosphonic acid and the product phosphorus-containing polyol of example 1;
FIG. 3 is an infrared spectrum of hydroxyethylidene diphosphonic acid and the product phosphorus-containing polyol of example 1;
FIG. 4 is a thermogravimetric analysis of the product phosphorus-containing polyol of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The experimental methods described in the examples are all conventional methods if not specifically stated; the reagents and materials are commercially available, unless otherwise specified.
Method for measuring acid value
Weighing a certain amount of sample 3g in a triangular flask by using an analytical balance, adding about 50mL of absolute ethyl alcohol, fully shaking the conical flask to completely dissolve the sample, heating if necessary, adding 5 drops of self-made phenolphthalein indicator, uniformly shaking, and adding KOH-CH with the concentration of 0.02mol/L 3 CH 2 The OH standard titration solution titrated it to a peach red colour while maintaining the 30s fadeless position while a blank test was run.
Calculating the formula:
AV: acid value, mg KOH/g;
V 1 : consumption of Potassium hydroxide-C during titration of a sample 2 H 5 Volume of OH standard solution, mL;
V 2 : potassium hydroxide-C consumed in titration of blanks 2 H 5 Volume of OH standard solution, mL;
c: concentration of potassium hydroxide-C2H 5OH standard solution, mol/L;
m: mass of sample, g;
56.1: molar mass of KOH, g/mol;
hydroxyl value measuring method
The measurement was carried out in accordance with "determination of hydroxyl value in polyester polyol HG/T2709-95". And (3) performing acylation reaction on hydroxyl in the sample and acetic anhydride in the acetylation reagent, adding water to decompose residual acetic anhydride, titrating the generated acetic acid by using a 0.5mol/L potassium hydroxide-ethanol standard titration solution, simultaneously performing a blank test, and calculating the hydroxyl value of the sample according to the difference value.
Formula for calculation
An OHV: hydroxyl number of the sample, mg KOH/g;
V A : the volume of the sodium hydroxide standard solution consumed in the blank experiment, mL;
V B : the volume of sodium hydroxide standard solution consumed by the sample, mL;
c: the molar concentration of the sodium hydroxide standard solution, mol/L;
m: sample mass, g;
56.1: molar mass of KOH, g/mol;
AV: acid value of sample, mg KOH/g.
Example 1
10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid is added into a 100mL four-neck flask provided with a constant pressure dropping funnel, a magneton, a thermometer and a reflux condenser tube, then 34.85g (0.60 mol) of propylene oxide is added dropwise, the temperature is kept for 6h under the normal pressure at 55 ℃, after the reaction is finished, an oil pump is used for reducing the pressure and pumping off the redundant propylene oxide, and colorless transparent viscous liquid is obtained, the acid value of the liquid is 0.80mg KOH/g, and the hydroxyl value of the liquid is 420mg KOH/g. The physical diagram of the product of this example 1 is shown in FIG. 1 (a), which demonstrates that the phosphorus-containing polyol prepared has high quality and good color.
The nuclear magnetic hydrogen spectrum and the infrared spectrum of the product are shown in figures 2 and 3.
The phosphorus-containing polyol prepared in this example has the following structure:
n 1 、n 2 、n 3 、n 4 are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 ≤12。
FIG. 2 (a) is a nuclear magnetic hydrogen spectrum of hydroxyethylidene diphosphonic acid. The multiplet at 1.45ppm in the figure is the absorption peak for methyl.
FIG. 2 (b) is a nuclear magnetic hydrogen spectrum of the phosphorus-containing polyol prepared in example 1 of the present invention. In the figure, a multiple peak a of 1.12ppm is H of a methyl group in a repeating unit, a single peak b near 1.35ppm is assigned to H of a methyl group in a main chain structure, a multiple peak near 3.47ppm is assigned to H of a methine group in a repeating structural unit, a multiple peak near 3.96ppm is assigned to H of a methylene group in a repeating structural unit, and a single peak near 4.19ppm is assigned to active hydrogen of a hydroxyl group.
The successful synthesis of the phosphorus-containing polyol prepared in example 1 can be demonstrated by comparison of nuclear magnetic hydrogen spectroscopy and infrared spectroscopy.
The thermogravimetric analysis of the phosphorus-containing polyol synthesized in this example is shown in FIG. 4. FIG. 4 illustrates that the phosphorus-containing polyol, having a decomposition temperature matched to that of the polyurethane, is suitable for use as a flame retardant for polyurethane foams.
Example 2
Adding 10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid into a high-pressure reaction kettle, then adding 22.03g (0.50 mol) of ethylene oxide, opening an air inlet valve of the reaction kettle, adjusting the control pressure of a nitrogen pressure reducing valve to be 0.5MPa, setting the temperature to be 70 ℃, reacting for 5 hours, and after the reaction is finished, pumping out the redundant ethylene oxide to obtain colorless transparent viscous liquid, wherein the acid value is 0.88mg KOH/g, and the hydroxyl value is 390mg KOH/g.
The phosphorus-containing polyol prepared in this example has the following structure:
n 1 、n 2 、n 3 、n 4 are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 ≤12。
Example 3
10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid is added into a 100mL four-neck flask provided with a constant pressure dropping funnel, a magneton, a thermometer and a reflux condenser tube, then 37.01g (0.40 mol) of epoxy chloropropane is added dropwise, the temperature is kept at the temperature of 95 ℃ under normal pressure for 7h, after the reaction is finished, an oil pump is used for reducing the pressure and pumping off the redundant epoxy chloropropane to obtain yellowish transparent viscous liquid, the acid value of which is 1.76mg KOH/g, and the hydroxyl value of which is 420mg KOH/g.
The phosphorus-containing polyol prepared in this example has the following structure:
example 4
10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid is added into a 100mL four-neck flask provided with a constant pressure dropping funnel, a magneton, a thermometer and a reflux condenser tube, 41.09g (0.30 mol) of propylene bromide epoxide is added dropwise, after the addition is finished, the temperature is kept at 95 ℃ for 8h under normal pressure, after the reaction is finished, the temperature is raised, and an oil pump is used for reducing the pressure and pumping off the redundant propylene bromide epoxide to obtain colorless transparent viscous liquid, wherein the acid value is 1.00mg KOH/g, and the hydroxyl value is 385mg KOH/g.
Example 5
10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid is added into a 100mL four-neck flask provided with a constant pressure dropping funnel, a magneton, a thermometer and a reflux condenser tube, 36.089g (0.50 mol) of 1, 1-dimethyloxirane is added dropwise, after the addition is finished, the temperature is kept at 55 ℃ under normal pressure for 6h, after the reaction is finished, the temperature is raised, and an oil pump is used for reducing the pressure and pumping off the redundant 1, 1-dimethyloxirane to obtain light yellow transparent viscous liquid, wherein the acid value is 0.35mg KOH/g, and the hydroxyl value is 370mg KOH/g.
The phosphorus-containing polyol prepared in this example has the following structure
Example 6
A mixed solution of 2.5g (0.012 mol) of hydroxyethylidene diphosphonic acid and 20g of 1, 4-dioxane is added into a 100mL four-necked flask provided with a thermometer, a condensation pipe, a mechanical stirring device and a dropping funnel, the temperature of the solution is raised to 95 ℃, after the reaction system is refluxed for 20min, 21g (0.084 mol of epoxy group) of epoxy soybean oil is started to be dropwise added, after the dropwise addition is finished, the reaction is carried out for 9h at the normal pressure of 95 ℃, after the reaction is finished, the solvent is removed by reduced pressure distillation at the temperature of 80 ℃, and viscous liquid is obtained, the acid value of the viscous liquid is 2.00mg KOH/g, and the hydroxyl value of the viscous liquid is 203mg KOH/g. A schematic diagram of the product of this example 6 is shown in FIG. 1 (b).
Example 7
Adding a mixed solution of 2.00g (0.01 mol) of hydroxyethylidene diphosphonic acid and 20g of toluene into a 100mL four-neck flask provided with a thermometer, a condenser pipe, a mechanical stirring device and a dropping funnel, raising the temperature of the solution to 90 ℃, starting to dropwise add 18.30g (0.07 mol of epoxy group) of epoxy cottonseed oil after a reaction system is refluxed for 20min, keeping the temperature at 90 ℃ under normal pressure for reaction for 8h after the dropwise addition is finished, and distilling under reduced pressure at 80 ℃ to remove the solvent after the reaction is finished to obtain a light yellow viscous liquid, wherein the acid value of the liquid is 1.59mg KOH/g, and the hydroxyl value of the liquid is 170mg KOH/g.
Example 8
Adding a mixed solution of 1.50g (0.007 mol) of hydroxyethylidene diphosphonic acid and 15g of isopropanol into a 100mL four-neck flask provided with a thermometer, a condenser, a mechanical stirring device and a dropping funnel, heating the solution to 80 ℃, starting to dropwise add 25g (0.049 mol of epoxy group) epoxy castor oil after a reaction system is refluxed for 20min, keeping the temperature at 80 ℃ under normal pressure for reaction for 9h after the dropwise addition is finished, and distilling at 80 ℃ under reduced pressure to remove the solvent after the reaction is finished to obtain a light yellow viscous liquid, wherein the acid value of the liquid is 1.08mg KOH/g, and the hydroxyl value of the liquid is 157mg KOH/g.
Example 9
Adding a mixed solution of 2.00g (0.01 mol) of hydroxyethylidene diphosphonic acid and 20g of isopropanol into a 100mL four-neck flask provided with a thermometer, a condenser pipe, a mechanical stirring device and a dropping funnel, heating the solution to 80 ℃, starting to dropwise add 22g (0.07 mol of epoxy group) epoxy tung oil after a reaction system is refluxed for 20min, keeping the temperature at 85 ℃ under normal pressure for reaction for 9h after the dropwise addition is finished, and distilling under reduced pressure at 80 ℃ to remove the solvent after the reaction is finished to obtain a light yellow viscous liquid, wherein the acid value of the liquid is 0.78mg KOH/g, and the hydroxyl value of the liquid is 175mg KOH/g.
Comparative example 1
10.30g (0.05 mol) of hydroxyethylidene diphosphonic acid is added into a 100mL four-neck flask provided with a constant pressure dropping funnel, a magneton, a thermometer and a reflux condenser tube, then 23.23g (0.40 mol) of propylene oxide is added dropwise, the temperature is kept at 10 ℃ under normal pressure for 6h, after the reaction is finished, excess propylene oxide is pumped out by using an oil pump under reduced pressure, and colorless transparent viscous liquid is obtained, wherein a large amount of undissolved solid is contained, and the acid value is 61.37mg KOH/g.
As can be seen from comparative example 1 and example 1, when hydroxyethylidene diphosphonic acid is reacted with propylene oxide at low temperature, the acid value of the product is too high and the reaction is incomplete.
Example 10
Application of reactive phosphorus-containing polyol flame retardant in polyurethane foam
The flame retardant (HEDP-PO) in example 1 was used in an amount of 0 to 50 parts by weight, and the formulation shown in Table 1 (each represents part by weight).
TABLE 1 polyurethane foam formulations
Wherein R represents the isocyanate index, which is the ratio of the equivalents of isocyanate to the equivalents of polyol.
All foams were prepared according to the same procedure. Table 1 shows the formulations of the raw materials of the foams, and the foams prepared according to the HEDP-PO content of 0, 10, 20, 30, 40 and 50 parts by weight in the mixed polyol are respectively named as PUF-0, PUF-1, PUF-2, PUF-3, PUF-4 and PUF-5. Rigid polyurethane foams (RPUF) were prepared by a one-step free rise process as shown in Table 1. Polyether polyol 4110, the flame retardant of example 1, catalyst DBTDL, distilled water and foam leveler AK8805 were premixed at room temperature to obtain a homogeneous polyol blend, then the calculated amount of isocyanate was added to the polyol blend (the amount added was calculated according to R), the resulting blend was poured into an open mold to foam after stirring for 10s and left for one week to complete curing, and finally the foam was cut to specific dimensions for characterization. The foams were tested and the results are shown in tables 2 and 3.
The Limiting Oxygen Index (LOI) is the minimum oxygen concentration required for a material to burn under a particular condition in a mixed stream of oxygen and nitrogen, thereby judging how easily the material burns in air. The higher the oxygen index of the material, the less readily combustible it is, generally the LOI <22% is combustible, the LOI between 22 and 27% is combustible, and the LOI >27% is nonflammable.
The vertical burning test (UL-94) refers to a test method in which a test specimen of a certain size is vertically arranged under a prescribed condition by applying a flame thereto and then classified according to the phenomenon of burning. UL-94 flame retardant ratings may be generally classified as V-0, V-1, and V-2, with the V-0 rating being the highest.
(1) The Limiting Oxygen Index (LOI) is measured by a JF-3 oxygen index tester of Jiangning district analytical instrument factory in Nanjing according to GB/T2406-1993 standard, and the size requirement of the foam is 130mm multiplied by 6.5mm multiplied by 3.0mm.
(2) The vertical burning (UL-94) is measured by a CZF-5 type horizontal vertical burning tester according to the GB/T2408-2008 standard, and the size requirement of the foam is 130mm multiplied by 13.0mm multiplied by 3.0mm.
(3) The apparent density of the foam was tested according to the method of GB/T6343-2009.
(4) The compression strength is tested according to GB/T8813-2008, the sample specification is 5cm multiplied by 5cm, the test speed is 10mm/min, the compression deformation is 10 percent
TABLE 2 flame retardancy Properties of polyurethane foams
As can be seen from Table 2, as the amount of the flame retardant added increases, the phosphorus content in the system increases, and the limiting oxygen index of the material therefore gradually increases. When the addition amount of the flame retardant is 30 parts (PUF-3), the limiting oxygen index reaches 25%, and the foam passes the UL-94 vertical combustion test and is V-0 grade; when the addition amount reaches 50 parts, the limited oxygen index reaches 28%, and the combustion grade is V-0 grade, which shows that the flame retardant has good flame retardant property.
TABLE 3 mechanical Properties of polyurethane foams
| Sample (I) | PUF-0 | PUF-1 | PUF-2 | PUF-3 | PUF-4 | PUF-5 |
| Apparent density (kg/m) 3 ) | 47.0 | 48.1 | 49.0 | 51.1 | 50.7 | 49.6 |
| Compressive Strength (MPa) | 0.167 | 0.172 | 0.191 | 0.215 | 0.220 | 0.212 |
Compared with the rigid polyurethane foam without adding the flame retardant PUF-0, the mechanical property of the rigid polyurethane foam is greatly improved after the flame retardant prepared in example 1 is added, because the flame retardant prepared in example 1 has a specific hydroxyl value and functionality, the crosslinking density of the prepared polyurethane foam is increased, and the compression strength of the polyurethane foam is gradually increased. Another possible reason is that the phosphate groups are flexible groups which can play a plasticizing role in the polyurethane. In fact, the mechanical properties of the polyurethane foam are affected by adding the flame retardant into the polyurethane foam, and the mechanical properties are affected more greatly by adding more flame retardant, and the mechanical properties (such as compressive strength) of the polyurethane foam are reduced by adding many reactive flame retardants in the prior art (see table 4 for details). The polyester foam such as PUF-3 and PUF-4 prepared by the specific flame retardant prepared by the invention not only does not influence the mechanical property of the polyester foam, but also can improve the mechanical property of the polyester foam, and the flame retardant level can reach V-0 level, so that the effect is very obvious. In the invention, the mechanical property of the PUF-5 is slightly reduced compared with that of the PUF-4 due to the higher addition amount of the flame retardant, but the mechanical property of the PUF-5 is still better than that of the PUF-4 without the flame retardant, and the flame retardant level can also reach V-0 level. Table 4 shows that the use of HEDP-PO polyol as a flame retardant exhibits better performance than previous flame retardants.
Table 4 effect of flame retardant addition on mechanical properties of polyurethane foams in the prior art.
Document 1: preparation and performance research of the flame-retardant soybean oil-based polyurethane rigid foam, a bachao of the university of Chilobrachys, hubei, 5 months in 2019.
Document 2: the synthesis of the triazine ring structure-containing polyol and the application thereof in polyurethane are shown in Schoendor's paper of Hubei university, 5 months 2020.
Document 3: research on flame retardant rigid polyurethane foams, von yuelan, chemical propellants and polymers, 2016, vol 14, no. 4.
Document 4: preparation and performance research of flame-retardant rigid polyurethane foam plastic, liufengjiao, a master academic paper of Beijing chemical university, 6 months in 2014.
Claims (9)
1. A phosphorus-containing polyol, wherein the phosphorus-containing polyol has the following structural formula:
wherein R is 1 is-H, -CH 3 ，-C 2 H 5 -any one of Ph, R 2 Is an epoxidized vegetable oil, an aliphatic alkoxy radical or a halogenated aliphatic alkoxy radical, where n 1 、n 2 、n 3 、n 4 Is R 2 Number of substituents, n 1 、n 2 、n 3 、n 4 Are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 ≤12。
2. The phosphorus-containing polyol according to claim 1, wherein when R is 2 When it is an aliphatic alkanoyloxy group or a halogenated aliphatic alkoxy group, n 1 、n 2 、n 3 、n 4 Are all positive integers more than or equal to 1, and n 1 +n 2 +n 3 +n 4 12 or less, wherein the aliphatic alkoxy or haloalkylic aliphatic alkoxy is any of the following groups:
3. the phosphorus-containing polyol of claim 1, wherein when R is 2 In the case of epoxidized vegetable oils, n 1 、n 2 、n 3 、n 4 1 and is any one of the following epoxidized vegetable oils:
epoxidized soybean oil, epoxidized castor oil, epoxidized corn oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized tung oil, and epoxidized methyl soyate.
4. A process for the preparation of a phosphorus-comprising polyol as claimed in claim 1, comprising the steps of:
adding polybasic phosphonic acid into a reaction device, then dropwise adding an epoxy compound, and after dropwise adding is finished, starting heat-preservation reaction at the reaction temperature of 55-95 ℃ for 3-9h; when the epoxy compound is epoxy vegetable oil, an organic solvent is required to be added.
5. The process according to claim 4, wherein said polyphosphonic acid is preferably hydroxyethylidene diphosphonic acid.
6. The process according to claim 4, wherein the epoxy compound is one or more selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, 1-dimethyloxirane, glycidol, and epoxidized vegetable oils.
7. The preparation method according to claim 4, characterized in that the solvent is any one or more of 1, 4-dioxane, isopropanol, tert-butanol, toluene, ethyl acetate, tetrahydrofuran.
8. The process according to claim 4, wherein the molar ratio of polyphosphonic acid to epoxy compound is 1: (4 to 14).
9. The production method according to claim 4, wherein the reaction apparatus is an atmospheric pressure reaction apparatus or a high pressure reaction apparatus, and if the high pressure reaction apparatus is used, nitrogen gas is introduced until the pressure in the reactor is 0.2 to 1MPa.
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