CN109970799A - Laccol base phosphorus-containing polyol and its preparation method and application - Google Patents
Laccol base phosphorus-containing polyol and its preparation method and application Download PDFInfo
- Publication number
- CN109970799A CN109970799A CN201910160504.2A CN201910160504A CN109970799A CN 109970799 A CN109970799 A CN 109970799A CN 201910160504 A CN201910160504 A CN 201910160504A CN 109970799 A CN109970799 A CN 109970799A
- Authority
- CN
- China
- Prior art keywords
- polyol
- structural formula
- laccol
- group
- laccol base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- DXRKLUVKXMAMOV-UHFFFAOYSA-N 3-heptadecylcatechol Chemical compound CCCCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DXRKLUVKXMAMOV-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229920005862 polyol Polymers 0.000 title claims abstract description 66
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 60
- 239000011574 phosphorus Substances 0.000 title claims abstract description 60
- 150000003077 polyols Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000004814 polyurethane Substances 0.000 claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 239000003063 flame retardant Substances 0.000 claims abstract description 42
- 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 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- -1 ethers compound Chemical class 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 claims description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical class CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000011496 polyurethane foam Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 claims 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 150000002170 ethers Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 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 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003500 flue dust Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PBONCSGLBNLRPG-UHFFFAOYSA-N isocyanoazaniumylidynemethane Chemical compound [C-]#[N+][N+]#[C-] PBONCSGLBNLRPG-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- 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
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
This application discloses a kind of laccol base phosphorus-containing polyols and preparation method thereof, and the flame retardant polyurethane being prepared by the laccol base phosphorus-containing polyol.The laccol base phosphorus-containing polyol includes at least one of the compound with structural formula shown in formula I.The laccol base phosphorus-containing polyol, it is as response type laccol base phosphorus-containing polyol, chemical reaction can occur with polyisocyanates and generate carbamate groups, ignition-proof element phosphorus is introduced into polymer network in the form of covalent bond, netted space polymers are formed, the polyurethane material of excellent fireproof performance is prepared.
Description
Technical field
This application involves a kind of laccol base phosphorus-containing polyols and its preparation method and application, belong to Organic chemical products technology
Field.
Background technique
Since polyurethane material has incendive hydrocarbon segment in structure, burning and difficult self-extinguishment, combustion are easy when meeting fire
A large amount of flue dust and toxic gas are generated when burning, human health and environment peace can also be jeopardized by bringing to fire extinguishing while difficulty
Entirely.Therefore, to be more widely applied polyurethane material, suitable component and dosage must just be added according to the requirement of material
Flame-retardant additive.However, additive flame retardant is more apparent to mechanical property, bad with polyurethane mixed performance, fire retardant is easy
It is precipitated.Chinese patent CN106117600A discloses a kind of reactive flame retardant THPP, which has preferable phosphorus content
And carbon left, there are the characteristics such as flame retarding efficiency height and Halogen, low cigarette, low toxicity, durability.Chinese patent CN104448202A is disclosed
A kind of phosphor-containing flame-proof method for preparing thermoplastic polyurethane elastomer, the disclosure technology are 1500~2500 to contain with molecular weight
Phosphorus polyester diol is raw material, and ignition-proof element phosphorus is introduced in polyurethane elastomer material strand, reduces inorganic fire retardants
Addition, so that the fire-retardant oxygen index (OI) of material is increased to 32 by 19, flame retardant property is good.
Since hydrolysis easily occurs for the ester bond in polyester, the polyurethane water resistance as obtained by polyester polyol is caused to owe
It is good.In many application fields, for polyurethane, it is often necessary to this class feature.For example, for can be by polyether polyol system
Standby polyurethane, it is desirable to assign its excellent anti-hydrolytic performance, as Chinese patent CN103703052B disclose it is a kind of prepare it is poly-
The method of ether carbonate polyalcohol, the polyether carbonate polyol as made from the technology are applied to polyurethane field with excellent
Performance.Wherein in the first step, by one or more H- function starter substances, by one or more alkylene oxygen and carbon dioxides
Polyether carbonate polyol is prepared in the presence of at least one DMC- catalyst, and in second step, it is different at least two
The mixture of alkylene oxide carries out chain to polyether carbonate polyol in the presence of at least one DMC- catalyst.For another example China is special
Sharp CN103314031B discloses a kind of hydrophobic polyether ester polyol, and the polyester ether polylol as made from the technology is applied to poly-
Urethane field has excellent anti-hydrolytic performance.
To sum up, by the introducing response type phosphonium flame retardant in polyurethane material, the phosphorus content in material can be increased, from
And improve the flame retardant property of material.However, not yet being provided to how making so far in flame retardant polyurethane field of material preparation
Any solution or at least satisfactory solution of standby laccol base phosphorus-containing polyol problem.
Summary of the invention
According to the one aspect of the application, a kind of laccol base phosphorus-containing polyol is provided, is contained as response type laccol base
Phosphorus polyalcohol can occur chemical reaction with polyisocyanates and generate carbamate groups, by ignition-proof element phosphorus with covalent bond
Form introduces polymer network, forms netted space polymers, the polyurethane material of excellent fireproof performance is prepared.
Laccol base phosphorus-containing polyol provided by the present application includes at least one in the compound with structural formula shown in formula I
Kind:
Wherein, R01Including straight chain C15Alkyl；
R02, R03, R04Independently selected from one of hydrogen, alkyl；
R1 05, R1 06, R1 07, R1 08, R1 09, R1 10, R1 11, R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12Independently
Selected from hydrogen, C1~C4One of alkyl.
In some specific examples, R02, R03, R04It can be independently selected from hydrogen, methyl, ethyl, propyl, normal-butyl, different
Any one of butyl；R1 05, R1 06, R1 07, R1 08, R1 09, R1 10, R1 11, R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11,
R2 12Independently selected from one of hydrogen, methyl, ethyl, propyl, normal-butyl, isobutyl group.
Optionally, R01Selected from straight chain C15Alkyl, straight chain C15One of alkenyl.
Optionally, the R01Selected from the group with formula (a) structural formula, the group with structural formula shown in formula (b),
One of group with structural formula shown in formula (c), group with structural formula shown in formula (d):
Optionally, the R1 05With R2 05It is identical group, the R1 06With R2 06It is identical group, the R1 07With R2 07
It is identical group, the R1 08With R2 08It is identical group, the R1 09With R2 09It is identical group, the R1 10With R2 10It is
Identical group, the R1 11With R2 11It is identical group, the R1 12With R2 12It is identical group.
Preferably, the R02, R03, R04Independently selected from one of hydrogen, methyl, the R1 05, R1 06, R1 07, R1 08,
R1 09, R1 10, R1 11, R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12Independently selected from one of hydrogen, methyl.
It is highly preferred that the R02, R03, R04Independently selected from hydrogen, the R1 05, R1 06, R1 07, R1 08, R1 09, R1 10, R1 11,
R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12Independently selected from hydrogen.
Specifically, as the R02, R03, R04Independently selected from hydrogen, the R1 05, R1 06, R1 07, R1 08, R1 09, R1 10, R1 11,
R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12When independently selected from hydrogen, the laccol base phosphorus-containing polyol is selected from tool
There is at least one of the compound of structural formula shown in formula I -1:
According to the another aspect of the application, a kind of system of laccol base phosphorus-containing polyol described in any of the above embodiments is additionally provided
Preparation Method, comprising steps of by the raw material a containing laccol base bisglycidyl ethers compound, the key compound containing P-OH, with catalysis
Agent a haptoreaction is to get the laccol base phosphorus-containing polyol.
Optionally, the laccol base bisglycidyl ethers compound is in the compound with structural formula shown in formula II
At least one:
R'01Selected from straight chain C15One of alkyl；R'02, R'03, R'04Independently selected from one of hydrogen, alkyl.
Optionally, R'01Selected from straight chain C15Alkyl, straight chain C15One of alkenyl.
Optionally, R'01Selected from the group with formula (a) structural formula, the group with structural formula shown in formula (b), tool
There are one of the group of structural formula shown in formula (c), the group with structural formula shown in formula (d):
Optionally, R'02, R'03, R'04Independently selected from one of hydrogen, methyl.
Preferably, R'02, R'03, R'04Independently selected from hydrogen.
Specifically, in one example, work as R'02, R'03, R'04When independently selected from hydrogen, the choosing of laccol base bisglycidyl ether
From at least one of the compound with structural formula shown in formula II -1:
In this application, those skilled in the art can select suitable laccol base bisglycidyl according to actual needs
Ether preparation method.Preferably:
The preparation method of laccol base bisglycidyl ether as shown in formula II, at least includes the following steps:
Laccol and epoxy chloropropionate is added in the four-hole boiling flask equipped with blender, reflux condensing tube, thermometer, dropping funel
Alkane is heated to 50~60 DEG C, and catalyst b is added dropwise dropwise under stiring, after being added dropwise, is warming up to 60~70 DEG C, and constant temperature is anti-
It answers 1~8 hour, obtains the mixture containing the double shrink drier oil ethers of laccol.Into the mixture containing laccol bisglycidyl ether
Organic solvent I and water washing is added, stratification removes water layer inorganic matter, washs repeatedly, is evaporated under reduced pressure, obtains structural formula such as
Laccol base bisglycidyl ether shown in formula II.Wherein, laccol, which is selected from, has at least one of compound shown in formula IV:
Wherein, R "01Including the group with formula (a) structural formula, the group with structural formula shown in formula (b), have
One of the group of structural formula shown in formula (c), group with structural formula shown in formula (d):
The laccol is to extract to obtain from natural raw lacquer through dimethylbenzene, acetone or alcohol；The natural raw lacquer is selected from
At least one of safe and comfortable paint, flat interest paint, entrance of the city paint, hair dam paint, Qinling Mountains paint or other raw lacquer.
The catalyst b is selected from least one of the solution of hydroxide containing alkali metal.
Preferably, the hydroxide of alkali metal is selected from least one of sodium hydroxide, potassium hydroxide.
Preferably, the molar concentration of the hydroxide solution containing alkali metal is 5~15mol/L；It is highly preferred that institute
The molar concentration for stating the hydroxide solution containing alkali metal is 10mol/L.
Optionally, the mole ratio of structural formula laccol as shown in formula IV and catalyst b are 1:1~4；Preferably,
The mole ratio of structural formula laccol as shown in formula IV and catalyst b are 1:1.5~3；It is highly preferred that the structural formula is such as
The mole ratio of laccol shown in formula IV and catalyst b are 1:2.
Optionally, the condition that catalyst b is added dropwise dropwise is 40~60 DEG C of dropwise additions 1~3 hour；Preferably, it is described by
The condition that catalyst b is added dropwise in drop is 50~60 DEG C and is added dropwise 2 hours.
Optionally, the organic solvent I in ethyl acetate, dimethylbenzene, toluene, tetrahydrofuran, dioxane extremely
Few one kind.
Optionally, the mass ratio of mixture and organic solvent I containing the double shrink drier oil ethers of laccol is 1:0.2~5；It is preferred that
The mass ratio on ground, mixture and organic solvent I containing the double shrink drier oil ethers of laccol is 1:0.5~2；It is highly preferred that containing paint
The mixture of the double shrink drier oil ethers of phenol and the mass ratio of organic solvent I are 1:1.
Optionally, the mass ratio of mixture and water containing the double shrink drier oil ethers of laccol is 1:0.2~5；Preferably, contain
The mixture of the double shrink drier oil ethers of laccol and the mass ratio of water are 1:0.5~2；It is highly preferred that containing the double shrink drier oil ethers of laccol
Mixture and water mass ratio be 1:1.
Optionally, the key compound containing P-OH is selected from least one of the compound with structural formula shown in formula III,
Wherein, R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently select hydrogen, C1~C4One of alkyl.
Preferably, R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently select hydrogen, methyl.
It is highly preferred that R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently select hydrogen.
For example, R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently selected from hydrogen, key compound containing P-OH
Selected from the compound with structural formula shown in formula III -1,
Optionally, the key compound containing P-OH is obtained using method comprising the following steps: will contain P-H key compound
With the reactant aqueous solution of peroxide, the key compound containing P-OH is obtained.
Optionally, the key compound containing P-OH is obtained using method comprising the following steps:
Under inert atmosphere, into the solution containing the key compound containing P-H, the aqueous solution of peroxide is added,
Through back flow reaction, the key compound containing P-OH is obtained.
Preferably, the inert atmosphere includes non-active gas, and the non-active gas is in nitrogen, inert gas
At least one；Solvent in the solution containing the key compound containing P-H be selected from dimethylbenzene, THF, DMF, DMSO,
At least one of DMAC, NMP；The quality of the key compound containing P-H: volume=1:2 of the aqueous solution of the peroxide
~4g/ml.
The reaction condition of preparation key compound containing P-OH is preferably: 50~100 DEG C of 8~30h of reaction time of reaction temperature.
It optionally, further include recrystallization when preparing key compound containing P-OH, after back flow reaction, the recrystallization includes benefit
It is recrystallized with isopropyl alcohol and water (volume ratio is 5~1:1).
Non-active gas is selected from least one of nitrogen, helium, neon, argon gas.
Optionally, described containing P-H key compound includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
(DOPO), at least one of dimethylphosphite；The aqueous solution of the peroxide includes aqueous hydrogen peroxide solution.
As a preferred embodiment, the method for preparing the key compound containing P-OH, includes at least step: filling
In the there-necked flask for having mechanical agitator, nitrogen inlet and spherical condensation tube, non-active gas protect atmosphere under, be added DOPO and
Then solvent is stirred to dissolve DOPO, aqueous hydrogen peroxide solution is added, and back flow reaction recrystallizes to get the chemical combination of key containing P-OH
Object.
Optionally, the molar ratio of the laccol base bisglycidyl ethers compound and the key compound containing P-OH is 1:
1~4.
Preferably, the molar ratio of the laccol base bisglycidyl ethers compound and the key compound containing P-OH is 1:
2。
Optionally, catalyst a includes tertiary amine；The condition of the reaction are as follows: 50~150 DEG C of reaction temperature, reaction time 2~
40h；Solvent in the raw material a is selected from least one of dimethylbenzene, THF, DMF, DMSO, DMAC, NMP.
Preferably, the condition of the reaction are as follows: 50~100 DEG C of reaction temperature, 10~30h of reaction time.
Preferably, the tertiary amine includes N, N- dimethyl benzyl amine, triethylamine, N, N- dimethyl cyclohexyl amine, N, N, N',
At least one of N'- tetramethyl Alkylenediamine, bis- (2- dimethylaminoethyl) ethers.
As a preferred embodiment, the preparation method of the laccol base phosphorus-containing polyol includes at least following step
It is rapid: laccol base bisglycidyl ethers compound and key compound containing P-OH to be dissolved in THF by mole ratio 1:1~4, in uncle
Under amine catalysis, the laccol base phosphorus-containing polyol is prepared in heating reaction.
According to the another aspect of the application, a kind of flame retardant polyurethane is additionally provided, the flame retardant polyurethane is by any of the above-described
Laccol base phosphorus-containing polyol described in, in the laccol base phosphorus-containing polyol being prepared according to method described in any of the above embodiments
At least one be prepared.
Present invention also provides the flame retardant polyurethane preparation methods, will contain the pure and mild polyisocyanate of laccol base phosphorus contained multicomponent
The raw material b of cyanate, with catalyst c haptoreaction, obtains the flame retardant polyurethane in anhydrous solvent.
Optionally, the polyisocyanates be selected from toluene di-isocyanate(TDI) (TDI), Isosorbide-5-Nitrae-tetramethylene diisocyanate,
1,6- hexamethylene diisocyanate (HDI), bis- isocyanide of ten dimethylene diisocyanate of 1,12-, hexamethylene -1,3- or 1,4-
Acid esters, isophorone diisocyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane two are different
Cyanate (HMDI), 1, hexamethylene-diisocyanate (HDI), polymethylene multi-phenenyl isocyanate (PAPI), phenylenedimethylidyne two
Isocyanates (XDI), naphthalene -1,5- diisocyanate (NDI), Methylcyclohexyl diisocyanate (HTDI), durol two are sub-
Methyl diisocyanate (TMXDI), hydrogenation methylenebis phenyl isocyanate (H12At least one of MDI).
Preferably, the polyisocyanates is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI)
(TDI), 1,6- hexamethylene diisocyanate (HDI), double-hexyl methane diisocyanate (HMDI), diphenyl methane 4,4-
Diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), hydrogenation methylenebis phenyl isocyanate (H12MDI at least one in)
Kind.
Optionally, the anhydrous solvent is selected from least one of DMF, DMSO, DMAC, NMP；
Catalyst c is selected from least one of organic tin salt；
The organic tin salt includes dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, two vinegar
Sour dibutyl tin；
The condition of the reaction are as follows: 50~120 DEG C of reaction temperature, 2~10h of reaction time.
Preferably, the condition of the reaction are as follows: 70~100 DEG C of reaction temperature, 3~5h of reaction time.
Optionally, also polynary comprising polyester polyol, polyether polyol, small molecule polyol, small molecule in the raw material b
At least one of amine；
Wherein, the small molecule polyol is selected from C1~C6At least one of polyalcohol；The small molecule polyamine is selected from
C1~C6At least one of polyamine.
Optionally, the polyester polyol is selected from polycaprolactone polyol, polycarbonate glycol, dicarboxylic acids and dihydric alcohol
Deng at least one of the polyester polyol obtained by polycondensation reaction；
Optionally, the polyether polyol is selected from polyethylene glycol dihydric alcohol, polypropylene glycol diols, polytetrahydrofuran binary
At least one of alcohol.
Preferably, the molecular weight of the polyether polyol is 600~5000Da.
It is highly preferred that the molecular weight of the polyether polyol is 1000~3000Da.
Optionally, the pure and mild laccol base phosphorus-containing polyol of the polyether polyols is dissolved in anhydrous solvent, is warming up to 50
~120 DEG C, polyisocyanates and catalyst c is added, reacts 2~6 hours, obtains the flame retardant polyurethane.
Optionally, the mass parts ratio of the polyether polyol, laccol base phosphorus-containing polyol, polyisocyanates and catalyst c
For 10~50:5~50:2~100:0.1~0.3.
Preferably, the mass parts ratio of the polyether polyol, laccol base phosphorus-containing polyol, polyisocyanates and catalyst c
For 15~30:10~35:20~60:0.1~0.3.
According to the application's in another aspect, providing a kind of polyurethane products, containing by flame retardant polyurethane described above,
The flame retardant polyurethane being prepared according to method described in any of the above embodiments.
Optionally, the polyurethane products include in elastic polyurethane, polyurethane foam and aqueous polyurethane body extremely
Few one kind.
Present invention also provides a kind of polyurethane products described above in field of thermal insulation, encapsulation field, paint field, glues
Application in jelly field, field of leather.
In the application, " alkyl " refers to the group formed by losing any one hydrogen atom on hydrocarbon molecules.
In the application, " alkenyl " refers to by losing any one hydrogen on the hydrocarbon molecules containing at least one C=C
The group that atom is formed.
In the application, " alkyl " refers to the group formed by losing any one hydrogen atom on alkane compound molecule.Alkane
Hydrocarbon compound includes cycloalkane, linear paraffin, branched paraffin.
In the application, C15、C1~C4In subscript indicate the carbon atom number that group is included.For example, C1~C4Alkyl table
Show that carbon atom number is 1~4 alkyl, C15Alkyl indicates that carbon atom number is 15 alkyl.
In the application, THF indicate anhydrous tetrahydro furan, DMF indicate dimethylformamide, DMSO indicate dimethyl sulfoxide,
DMAC indicates that dimethyl acetamide, NMP indicate N-Methyl pyrrolidone.
In the application, " polyalcohol " refers to the compound containing at least two-OH.
In the application, " polyamine " refers to containing at least two-NR2Compound；R is selected from H, C1~C10Alkyl.
The beneficial effect that the application can generate includes:
1) laccol base phosphorus-containing polyol provided by the present application is used as response type laccol base phosphorus-containing polyol, energy and polyisocyanate
Cyanate occurs chemical reaction and generates carbamate groups, and ignition-proof element phosphorus is introduced polymeric web in the form of covalent bond
Network forms netted space polymers.
2) preparation method of laccol base phosphorus-containing polyol provided by the present application, this method is easy to operate, and raw material sources are extensive.
3) flame retardant polyurethane provided by the present application has excellent flame retardant properties, mechanical properties and anti-hydrolytic performance.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resoance spectrum hydrogen spectrogram of laccol base bisglycidyl ether in embodiment 1.
Fig. 2 is the nuclear magnetic resoance spectrum phosphorus spectrogram of laccol base phosphorus-containing polyol in embodiment 1.
Fig. 3 is the infrared spectrogram of laccol base phosphorus-containing polyol in embodiment 1.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, raw material employed in embodiment is all from commercially available, unprocessed direct use；Implement
Instrument and equipment employed in example is all made of manufacturer's recommended parameter.
Analysis instrument is as follows in embodiments herein:
Using AVANCE III HD (Bruker-BioSpin) nuclear magnetic resonance spectrometer carry out to products obtained therefrom in embodiment into
Row1H-NMR and31P-NMR characterization.Phosphorus stave levies condition as hydrogen decoupling, and pre- extension D1=10 seconds, scanning times were greater than 16 times, molten
Agent CDCl3。
Examination of infrared spectrum is carried out using Bruker VERTEX70 infrared spectrometer.
Miscellaneous -10- phospho hetero phenanthrene -10- the oxide of 9,10- dihydro-9-oxy is abbreviated as DOPO in the application.
1 laccol base phosphorus-containing polyol D1 of embodiment#Preparation
The synthesis and characterization of a1 laccol base bisglycidyl ethers compound
Equipped with blender, reflux condensing tube, thermometer, dropping funel four-hole boiling flask be added 0.3mol laccol and
The epoxychloropropane of 0.6mol is heated to 55 DEG C, and the NaOH solution 1.5 of the 10mol/L of 60ml is added dropwise dropwise under stiring
Hour, after being added dropwise, be warming up to 65 DEG C, and isothermal reaction 5 hours, obtain containing laccol pair shrink drier oil ether compound,
The mixture of water, sodium chloride.Dimethylbenzene and water washing are added into the mixture of the laccol bisglycidyl ethers compound, it is quiet
Overnight layering is set, water layer inorganic matter is removed, washs repeatedly, is evaporated under reduced pressure, is obtained laccol base bisglycidyl ethers compound, be denoted as
r1-1#,
To laccol base bisglycidyl ethers compound r1-1#Carry out nmr analysis, nuclear magnetic data are as follows:1H NMR/ppm
(CDCl3, MHz): δ=6.90-6.65 (3H), 5.7-4.7 (6H), 3.75-4.25 (4H), 3.70-3.50 (2H), 3.50-
2.50(10H),1.80–1.15(12H),0.9–0.8(3H)。
Its nuclear magnetic resoance spectrum hydrogen spectrogram is as shown in Figure 1；
Characterization result is shown: r1-1#Structural formula be
R'01For the group with formula (a) structural formula, the group with structural formula shown in formula (b), there is formula (c) institute
Show the group of structural formula and the group with structural formula shown in formula (d)；
The synthesis of b1 key compound containing P-OH and characterization
Equipped with mechanical agitator, nitrogen inlet and spherical condensation tube there-necked flask in, be added 100.0g DOPO and
600mL ethyl alcohol, after stirring and dissolving；Addition 300mL aqueous hydrogen peroxide solution, back flow reaction 12 hours.It is cooled to room temperature, rotation is steamed
Hair removes solvent, is then recrystallized with isopropyl alcohol and water (volume ratio v/v=3/1).Filtering, vacuum drying, the chemical combination of key containing P-OH
Object is denoted as r1-2#；
Nmr analysis, nuclear magnetic data are carried out to the r1-2# of key compound containing P-OH are as follows:1H NMR/ppm(CDCl3, MHz): δ=
8.05-7.40(8H)。
Characterization result is shown: r1-2#Structural formula be
The preparation and representation of c1 laccol base phosphorus-containing polyol
In the there-necked flask equipped with mechanical agitator and spherical condensation tube, under nitrogen protection, 0.2mol is added and contains P-OH
Key compound r1-2#With 300mL anhydrous tetrahydro furan (THF), after stirring and dissolving.By 0.1mol laccol base bisglycidyl ethers
Compound r1-1#With 6.5mmol N, N- dimethyl benzyl amine is added in solution, is reacted 24 hours at 70 DEG C.It is cooled to room
Temperature, rotary evaporation remove solvent, are washed with n-hexane, and vacuum drying obtains laccol base phosphorus-containing polyol, are denoted as D1#；
To laccol base phosphorus-containing polyol D1#Carry out nmr analysis, nuclear magnetic data are as follows:31P NMR/ppm(CDCl3,MHz):δ
=34.
Nuclear magnetic resoance spectrum phosphorus spectrogram as shown in Fig. 2, infrared spectrogram as shown in figure 3,
Characterization result is shown: laccol base phosphorus-containing polyol D1#Structural formula be
R01For the group with formula (a) structural formula, the group with structural formula shown in formula (b), have shown in formula (c)
The group of structural formula, the group with structural formula shown in formula (d),
2 laccol base phosphorus-containing polyol D2 of embodiment#Preparation
The synthesis of a2 laccol base bisglycidyl ethers compound
Equipped with blender, reflux condensing tube, thermometer, dropping funel four-hole boiling flask be added 0.3mol laccol and
The epoxychloropropane of 0.6mol is heated to 55 DEG C, and the KOH solution 2 that the 10mol/L of 30ml is added dropwise dropwise under stiring is small
When, after being added dropwise, be warming up to 65 DEG C, and isothermal reaction 4 hours, obtain containing the double shrink drier oil ether compound of laccol, water,
The mixture of sodium chloride.Dimethylbenzene and water washing are added into the mixture of the laccol bisglycidyl ethers compound, stands
Layering overnight removes water layer inorganic matter, washs repeatedly, is evaporated under reduced pressure, obtains laccol base bisglycidyl ethers compound, be denoted as
r2-1#；
The synthesis of b2 key compound containing P-OH
Equipped with mechanical agitator, nitrogen inlet and spherical condensation tube there-necked flask in, be added 100.0g DOPO and
600mLDMF, after stirring and dissolving；Addition 300mL aqueous hydrogen peroxide solution, back flow reaction 8 hours.It is cooled to room temperature, rotary evaporation
Solvent is removed, is then recrystallized with isopropyl alcohol and water (volume ratio v/v=3/1).Filtering, vacuum drying, key compound containing P-OH,
It is denoted as r2-2#；
The preparation of c2 laccol base phosphorus-containing polyol
In the there-necked flask equipped with mechanical agitator and spherical condensation tube, under nitrogen protection, 0.2mol is added and contains P-OH
Key compound r2-2#With 300mL dimethylbenzene, after stirring and dissolving.By 0.1mol laccol base bisglycidyl ethers compound r2-1#
With 6.5mmol N, N- dimethyl benzyl amine is added in solution, is reacted 6 hours at 140 DEG C.It is cooled to room temperature, rotary evaporation
Solvent is removed, is washed with n-hexane, vacuum drying obtains laccol base phosphorus-containing polyol, is denoted as D2#。
Laccol base bisglycidyl ether r2-1 obtained in the present embodiment#, the r2-2# of key compound containing P-OH, laccol base contain
Phosphorus polyalcohol D2#Nuclear magnetic data, nmr spectrum and corresponding infrared data and the test result phase in embodiment 1
With to get having arrived target product.
The preparation of 3 flame retardant polyurethane E1 of embodiment
10.0 grams of polytetrahydrofuran dihydric alcohols (PTMEG 2000) are added in 250mL a bite bottle and 5.0 grams of laccol bases contain
Phosphorus polyalcohol D1#, the dry anhydrous solvent DMF of 160mL is added, is warming up to 95 DEG C, 2 grams of polyisocyanates IPDI, catalyst c is added
Dibutyl tin dilaurate 2 drips, and reacts 4 hours, obtains flame retardant polyurethane, be denoted as E1.
The preparation of 4 flame retardant polyurethane E2 of embodiment
10.0 grams of polytetrahydrofuran dihydric alcohols (PTMEG 2000) are added in 250mL a bite bottle and 6.0 grams of laccol bases contain
Phosphorus polyalcohol D1#, the dry anhydrous solvent DMF of 160mL is added, is warming up to 80 DEG C, 1.7 grams of polyisocyanates MDI, catalyst is added
C dibutyl tin dilaurate 4 drips, and reacts 5 hours, obtains flame retardant polyurethane, be denoted as E2.
The preparation of 5 flame retardant polyurethane E3 of embodiment
10.0 grams of polytetrahydrofuran dihydric alcohols (PTMEG 2000) are added in 250mL a bite bottle and 6.5 grams of laccol bases contain
Phosphorus polyalcohol D2#, the dry anhydrous solvent DMF of 160mL is added, is warming up to 100 DEG C, 1.8 grams of polyisocyanates H is added12MDI is urged
Agent c dibutyl tin dilaurate 3 drips, and reacts 5 hours, obtains flame retardant polyurethane, be denoted as E3.
The preparation of 6 flame retardant polyurethane E4 of embodiment
10.0 grams of polytetrahydrofuran dihydric alcohols (PTMEG 2000) are added in 250mL a bite bottle and 6.6 grams of laccol bases contain
Phosphorus polyalcohol D2#, the dry anhydrous solvent DMF of 160mL is added, is warming up to 90 DEG C, 1.2 grams of polyisocyanates HDI, catalyst is added
C dibutyl tin dilaurate 3 drips, and reacts 4.5 hours, obtains flame retardant polyurethane, be denoted as E4.
The test of 7 flame retardant property of embodiment
Resistance according to the method in GB/T 2408-2008 standard (combustion testing standard) to flame retardant polyurethane sample E1-E4
Combustion performance is measured, and the results are shown in Table 1.
Table 1
| Sample number into spectrum | Flame retardant test result (UL-94) |
| E1 | V-0 |
| E2 | V-0 |
| E3 | V-0 |
| E4 | V-0 |
From table 1 it follows that the flame retardant polyurethane material E1-E4 being prepared has excellent flame retardant effect.
8 Mechanics Performance Testing of embodiment
Mechanics Performance Testing is carried out to flame retardant polyurethane sample E1-E4；Wherein, the measurement of tensile property is according to GB/
Method measures in T13022-91.Test result is as shown in table 2.
Table 2
From Table 2, it can be seen that the flame retardant polyurethane material E1-E4 being prepared has excellent mechanical property.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of laccol base phosphorus-containing polyol, which is characterized in that include at least one in the compound with structural formula shown in formula I
Kind:
Wherein, R01Selected from straight chain C15One of alkyl；
R02, R03, R04Independently selected from one of hydrogen, alkyl；
R1 05, R1 06, R1 07, R1 08, R1 09, R1 10, R1 11, R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12Independently selected from
Hydrogen, C1~C4One of alkyl；
Preferably, R01Selected from straight chain C15Alkyl, straight chain C15One of alkenyl；
Preferably, R01Selected from the group with formula (a) structural formula, the group with structural formula shown in formula (b), there is formula
(c) one of the group of structural formula shown in, group with structural formula shown in formula (d):
Preferably, the R1 05With R2 05It is identical group；The R1 06With R2 06It is identical group；The R1 07With R2 07It is phase
Same group；The R1 08With R2 08It is identical group；The R1 09With R2 09It is identical group；The R1 10With R2 10It is identical
Group；The R1 11With R2 11It is identical group；The R1 12With R2 12It is identical group；
Preferably, the R02, R03, R04Independently selected from one of hydrogen, methyl, the R1 05, R1 06, R1 07, R1 08, R1 09,
R1 10, R1 11, R1 12, R2 05, R2 06, R2 07, R2 08, R2 09, R2 10, R2 11, R2 12Independently selected from one of hydrogen, methyl；
Preferably, the laccol base phosphorus-containing polyol is selected from least one of the compound with structural formula shown in formula I -1；
2. the preparation method of laccol base phosphorus-containing polyol described in a kind of claim 1, which is characterized in that include at least following step
It is rapid:
By the raw material a containing laccol base bisglycidyl ethers compound and the key compound containing P-OH, contacted instead with catalyst a
It should be to get the laccol base phosphorus-containing polyol.
3. preparation method according to claim 2, which is characterized in that the laccol base bisglycidyl ethers compound choosing
From at least one of the compound with structural formula shown in formula II:
R'01Selected from straight chain C15One of alkyl；
R'02, R'03, R'04Independently selected from one of hydrogen, alkyl；
Preferably, R'01Selected from straight chain C15Alkyl, straight chain C15One of alkenyl；
Preferably, R'01Selected from the group with formula (a) structural formula, the group with structural formula shown in formula (b), there is formula
(c) one of the group of structural formula shown in, group with structural formula shown in formula (d):
Preferably, R'02, R'03, R'04Independently selected from one of hydrogen, methyl；
Preferably, the laccol base bisglycidyl ethers compound is in the compound with structural formula shown in formula II -1
It is at least one:
4. preparation method according to claim 2, which is characterized in that the key compound containing P-OH, which is selected from, has III institute of formula
Show at least one of the compound of structural formula,
Wherein, R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently select hydrogen, C1~C4One of alkyl；
Preferably, R'05, R'06, R'07, R'08, R'09, R'10, R'11, R'12Independently select one of hydrogen, methyl；
Preferably, the key compound containing P-OH is the compound with structural formula shown in formula III -1:
Preferably, the key compound containing P-OH is obtained using method comprising the following steps:
By the reactant aqueous solution of key compound containing P-H and peroxide, the key compound containing P-OH can be obtained；
Preferably, the key compound containing P-OH is obtained using method comprising the following steps:
Under inert atmosphere, into the solution containing the key compound containing P-H, the aqueous solution of peroxide is added, through returning
Stream reaction obtains the key compound containing P-OH；
Preferably, the inert atmosphere includes non-active gas, the non-active gas in nitrogen, inert gas extremely
Few one kind；
Solvent in the solution containing the key compound containing P-H is in dimethylbenzene, THF, DMF, DMSO, DMAC, NMP
At least one；
The quality of the key compound containing P-H: volume=1:2~4g/ml of the aqueous solution of the peroxide；
Preferably, the key compound containing P-H includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid two
At least one of methyl esters；
The aqueous solution of the peroxide includes aqueous hydrogen peroxide solution.
5. preparation method according to claim 2, which is characterized in that the laccol base bisglycidyl ethers compound with
The molar ratio of the key compound containing P-OH is 1:1~4；
Preferably, the molar ratio of the laccol base bisglycidyl ethers compound and the key compound containing P-OH is 1:2；
Preferably, the catalyst a includes tertiary amine；
The condition of the reaction are as follows: 50~150 DEG C of reaction temperature, 2~40h of reaction time；
Solvent in the raw material a is selected from least one of dimethylbenzene, THF, DMF, DMSO, DMAC, NMP；
Preferably, the condition of the reaction are as follows: 50~100 DEG C of reaction temperature, 10~30h of reaction time；
Preferably, the tertiary amine includes N, N- dimethyl benzyl amine, triethylamine, N, N- dimethyl cyclohexyl amine, N, N, N', N'- tetra-
At least one of methyl Alkylenediamine, bis- (2- dimethylaminoethyl) ethers.
6. a kind of flame retardant polyurethane, which is characterized in that the flame retardant polyurethane is by laccol base phosphorus contained multicomponent described in claim 1
The preparation of at least one of laccol base phosphorus-containing polyol that alcohol, method according to any one of claims 2 to 5 are prepared
It obtains.
7. a kind of preparation method of flame retardant polyurethane as claimed in claim 6, which is characterized in that will be phosphorous containing the laccol base
The raw material b of polyalcohol and polyisocyanates, with catalyst c haptoreaction, obtains the flame retardant polyurethane in anhydrous solvent；
Preferably, the polyisocyanates is selected from toluene di-isocyanate(TDI), Isosorbide-5-Nitrae-tetramethylene diisocyanate, 1,6-, six methylene
Group diisocyanate, ten dimethylene diisocyanate of 1,12-, hexamethylene -1,3- or 1,4- diisocyanate, isophorone two
Isocyanates, diphenyl methane 4,4- diisocyanate, double-hexyl methane diisocyanate, 1 are hexamethylene-diisocyanate, more
Polymethylene polyphenyl isocyanates, benzene dimethylene diisocyanate, naphthalene -1,5- diisocyanate, two isocyanide of methylcyclohexyl
At least one of acid esters, tetramethylxylylene diisocyanate, hydrogenation methylenebis phenyl isocyanate；
Preferably, the anhydrous solvent is selected from least one of DMF, DMSO, DMAC, NMP；
The catalyst c is selected from least one of organic tin salt；
The organic tin salt includes dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, two acetic acid two
Butyl tin；
The condition of the reaction are as follows: 50~120 DEG C of reaction temperature, 2~10h of reaction time；
Preferably, the condition of the reaction are as follows: 70~100 DEG C of reaction temperature, 3~5h of reaction time；
Preferably, also comprising in polyester polyol, polyether polyol, small molecule polyol, small molecule polyamine in the raw material b
At least one；
Wherein, the small molecule polyol is selected from C1~C6At least one of polyalcohol；
The small molecule polyamine is selected from C1~C6At least one of polyamine；
Preferably, the polyether polyol is in polyethylene glycol dihydric alcohol, polypropylene glycol diols, polytetrahydrofuran dihydric alcohol
At least one；
Preferably, the molecular weight of the polyether polyol is 600~5000Da；
Preferably, the molecular weight of the polyether polyol is 1000~3000Da；
Preferably, the pure and mild laccol base phosphorus-containing polyol of the polyether polyols is dissolved in anhydrous solvent, is warming up to 50~120
DEG C, polyisocyanates and catalyst c is added, reacts 2~6 hours, obtains the flame retardant polyurethane；
Preferably, the mass parts ratio of the polyether polyol, laccol base phosphorus-containing polyol, polyisocyanates and catalyst c are 10
~50:5~50:2~100:0.1~0.3；
Preferably, the mass parts ratio of the polyether polyol, laccol base phosphorus-containing polyol, polyisocyanates and catalyst c are 15
~30:10~35:20~60:0.1~0.3.
8. a kind of polyurethane products, which is characterized in that contain by flame retardant polyurethane as claimed in claim 6, according to claim 7
The flame retardant polyurethane that the method is prepared.
9. polyurethane products according to claim 8, which is characterized in that the polyurethane products include elastic polyurethane,
At least one of polyurethane foam and aqueous polyurethane body.
10. polyurethane products described in claim 8 or 9 field of thermal insulation, encapsulation field, paint field, adhesive field,
Application in field of leather.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785788A (en) * | 2023-01-29 | 2023-03-14 | 江苏零界科技集团有限公司 | Environment-friendly paint for wooden products and preparation method thereof |
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