CN114409863A - Trihydroxymethyl phosphine oxide modified isocyanate compound and synthesis method thereof - Google Patents
Trihydroxymethyl phosphine oxide modified isocyanate compound and synthesis method thereof Download PDFInfo
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- CN114409863A CN114409863A CN202210109284.2A CN202210109284A CN114409863A CN 114409863 A CN114409863 A CN 114409863A CN 202210109284 A CN202210109284 A CN 202210109284A CN 114409863 A CN114409863 A CN 114409863A
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- CN
- China
- Prior art keywords
- phosphine oxide
- isocyanate compound
- modified isocyanate
- trihydroxymethyl
- tris
- 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.)
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 63
- -1 isocyanate compound Chemical class 0.000 title claims abstract description 39
- DKRWGRQBYLWNKR-UHFFFAOYSA-N OC(O)(O)[PH2]=O Chemical compound OC(O)(O)[PH2]=O DKRWGRQBYLWNKR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 26
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 18
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 23
- 229910052736 halogen Inorganic materials 0.000 abstract description 14
- 150000002367 halogens Chemical class 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 239000006260 foam Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 230000000711 cancerogenic effect Effects 0.000 abstract description 5
- 231100000315 carcinogenic Toxicity 0.000 abstract description 5
- 150000004826 dibenzofurans Chemical class 0.000 abstract description 5
- 239000005556 hormone Substances 0.000 abstract description 5
- 229940088597 hormone Drugs 0.000 abstract description 5
- 239000012433 hydrogen halide Substances 0.000 abstract description 5
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 5
- 231100000021 irritant Toxicity 0.000 abstract description 5
- 239000002085 irritant Substances 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 150000002013 dioxins Chemical class 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 description 65
- 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 description 61
- 150000002513 isocyanates Chemical class 0.000 description 28
- 229920005862 polyol Polymers 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000004970 Chain extender Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000008094 contradictory effect Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MMGMYZMTUVIVSU-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Br)=CC(C(Cl)=O)=C1 MMGMYZMTUVIVSU-UHFFFAOYSA-N 0.000 description 2
- YFHCUNVROJHJHV-UHFFFAOYSA-N BrC=1C=C(C=C(C=1)N=C=O)N=C=O Chemical compound BrC=1C=C(C=C(C=1)N=C=O)N=C=O YFHCUNVROJHJHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 1
- JATKASGNRMGFSW-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(Br)=CC(C(O)=O)=C1 JATKASGNRMGFSW-UHFFFAOYSA-N 0.000 description 1
- 101000575029 Bacillus subtilis (strain 168) 50S ribosomal protein L11 Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102100035793 CD83 antigen Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000946856 Homo sapiens CD83 antigen Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-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
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a trihydroxymethyl phosphine oxide modified isocyanate compound and a synthesis method thereof, belonging to the technical field of polyurethane materials. The invention uses the polymerization of the trihydroxymethyl phosphine oxide and TDI to obtain the trihydroxymethyl phosphine oxide modified isocyanate compound. The modified isocyanate compound contains P element, does not contain halogen, and can greatly improve the flame retardance of the polyurethane foam without reducing the environmental protection index of the foam. The modified isocyanate compound developed by the invention does not contain halogen, has small combustion smoke quantity, does not release corrosive or irritant hydrogen halide gas, does not generate toxic carcinogenic substances such as polybrominated dioxin and polybrominated dibenzofuran, and does not contain an environmental hormone substance such as a halogen organic substance, thereby avoiding the long-term influence of materials on the environment.
Description
Technical Field
The invention relates to a trihydroxymethyl phosphine oxide modified isocyanate compound and a synthesis method thereof, belonging to the technical field of polyurethane materials.
Background
The annual total production of global polyurethane is about 2000 million tons, the national production accounts for about 55 percent of the world production, the product which is most widely applied and has the largest use amount is a foam product and accounts for about 40 percent of the product. The polyurethane foam products with the largest consumption are soft sponges for seats of vehicles such as mattresses, sofas, automobiles and the like and hard foams for heat preservation of buildings such as refrigerators, refrigeration houses, houses and the like, and the polyurethane foams in many application fields need to have good flame retardant capability and good environmental protection performances such as smell and TVOC.
On the one hand, flame retardance has become a bottleneck problem of polyurethane foam used in the fields of refrigeration houses, passenger cars, trains, public homes and the like. Polyurethane foam is inherently flammable as a foam if a flame retardant is not added. The combustion characteristic of the GB38262-2019 passenger car interior material is implemented in 7-1.7.2020, and the horizontal combustion of the polyurethane seat is regulated to be A0 grade, and the vertical combustion is less than or equal to 100 mm/min; the polyurethane thermal insulation noise reduction material needs oxygen index to meet 25 percent and 28 percent besides horizontal/vertical combustion. In the field of trains: the oxygen indexes of the flame retardant performance of the seats in high-speed rail and common trains respectively meet the requirements of 28 percent (the technical conditions of flame retardant of the built-in material for the motor train unit 2010 TBT 3237-.
Polyurethane foam is formed by reacting isocyanate and polyol two components, and most of the research for improving the flame retardance of polyurethane foam plastics at present focuses on the polyol component, and the following methods are mainly adopted:
1. the problems of strong plasticizing effect, flame retardant migration and the like exist when a phosphorus or halogen liquid flame retardant is added into the polyol component;
2. the development of the polyhydric alcohol with flame retardant elements such as phosphorus, nitrogen, halogen and the like has the problems of poor physical properties, undesirable flame retardant effect and high cost;
3. the flame retardant is realized by adding solid flame retardants such as expandable graphite, aluminum hydroxide and the like, and the product and process range is narrow.
The halogen flame retardant has large smoke quantity, the released hydrogen halide is corrosive or irritant, toxic carcinogenic substances such as polybrominated benzo-oxen and polybrominated dibenzofuran can be generated, most halogen organic substances are environmental hormone substances, and the organic substances can induce organism mutation to influence the immune system, the endocrine system and the reproductive system of a human body and influence the normal metabolism of the human body. The RoHS directive was implemented beginning on 7/1 of the european union 2006 to strictly limit the use of polybrominated diphenylether PBDE, polybrominated biphenylether PBB, and the requirements for the prohibition of the use of halogen flame retardants in electronic display housings and supports were issued on 12/5 of 2019.
On the other hand, environmental issues such as TVOC and odor are another bottleneck problem in polyurethane flame retardant foams for enclosed space applications such as in vehicles. For example, chinese article 2018.6.23 reports that "the rejuvenate number frequently suffers complaints of peculiar smell in the car, the medium-iron total: and (5) carrying out self-checking and strictly controlling raw material purchasing. Flame retardance and environmental protection are mutually contradictory indexes, and the flame retardant is one of the factors which have the greatest contribution to TVOC and smell.
The difficulty of the problem is that high flame retardance and low TVOC and low odor are two mutually contradictory indexes, because the physically added flame retardant is one of the factors which most contribute to the TVOC and odor of the flame-retardant soft foam.
Patents relating to flame retardant related modified isocyanates are: the invention discloses an invention patent with publication number CN105949435A, and relates to a self-flame-retardant waterborne polyurethane emulsion which is prepared from the following raw materials in parts by weight: 20-35 parts of polyester polyol or polyether polyol, 2-6 parts of dimethylolpropionic acid, 15-40 parts of isocyanate monomer containing halogen functional group, 2-10 parts of small molecular chain extender, 0.02-0.1 part of dibutyltin dilaurate, 2-5 parts of neutralizing agent triethylamine, 1-3 parts of organic amine chain extender and 80-150 parts of deionized water. Also provides a preparation method thereof: firstly, stirring, protecting with nitrogen, heating, adding a diluent, a micromolecular chain extender, dibutyltin dilaurate and the like to prepare a modified polyurethane prepolymer, then neutralizing, emulsifying and carrying out aqueous phase chain extension on the modified polyurethane prepolymer, and finally distilling the solvent under reduced pressure to obtain the self-flame-retardant waterborne polyurethane emulsion.
The invention patent application with publication number CN109970605A provides a bromine-containing diisocyanate with flame retardant properties, the structure name of which is 1-bromo-3, 5-diisocyanatobenzene, which can be applied to polyurea coatings as a flame retardant. The preparation method comprises the following steps: (1) reacting 5-bromo-isophthalic acid in SOCl2Refluxing, and then evaporating to remove SOCl under reduced pressure2To obtain 5-bromo-isophthaloyl dichloride; (2) 5-bromo-isophthaloyl chloride was dissolved in THF, followed by addition of NaN3Adding saturated NaHCO into the mixed solution3Extracting with toluene, drying the organic layer and evaporating under reduced pressure to obtain a toluene solution of 5-bromo-m-dibenzoyl diazide; (3) and refluxing the toluene solution of the 5-bromo-m-dibenzoyl diazide to remove toluene, thereby obtaining the 1-bromo-3, 5-diisocyanatobenzene.
The invention patent application with publication number CN112041364A relates to a two-component adhesive composition, useful for food packaging, pharmaceutical packaging and industrial lamination. The adhesive composition comprises (a) an isocyanate component and (B) an isocyanate-reactive component, wherein the isocyanate component (a) is based on a phosphate polyol modified isocyanate. And the adhesive composition is compatible with both conventional lamination techniques (i.e., pre-mixing the two components prior to application to the substrate) and relatively newer lamination techniques (i.e., applying the components to separate substrates and bringing the substrates together to mix the components).
The invention patent application with publication number CN112375207A provides a phosphorus-nitrogen modified isocyanate which can be directly used as a raw material to participate in the synthesis of a polyurethane material, and the preparation method comprises the following steps: (1) introducing inert gas, 27-35 parts of triallyl phosphate, 28-41 parts of hexamethyldisilazane (amine) alkane, 0.12-0.43 part of chloroplatinic acid and 220 parts of solvent, and heating and stirring to obtain silicon phosphate; (2) adding 180 parts of unsaturated isocyanate 100, 0.31-0.73 part of chloroplatinic acid and 2.5-4.5 parts of 1, 1' -bis (dimethylsilyl) ferrocene into silicon phosphate, and evaporating the solvent after reaction to obtain the phosphorus-nitrogen modified isocyanate.
The invention patent with publication number CN110184016A discloses a flame-retardant bi-component polyurethane adhesive for a new energy battery, which comprises A, B two components, wherein A comprises the following components: 55-85% of modified isocyanate prepolymer, 6-20% of flame retardant a, 8-22% of filler a and 1-3% of stabilizer; the composition of B: 30-75% of polyol, 3-10% of amine, 2-5% of coupling agent, 78-30% of flame retardant b10 and 25% of filler b 10. The weight ratio of the component A to the component B is 1: 1. The modified isocyanate prepolymer comprises the following components in parts by weight: 120-180 parts of isocyanate, 30-70 parts of dihydric alcohol, 60-100 parts of phosphorus flame retardant containing hydroxyl, 0.05-1 part of dibutyltin dilaurate and 0.05-5 parts of polymerization inhibitor; the flame retardant a and the flame retardant b are independently selected from one of cresyldiphenyl phosphate, isopropylated triphenyl phosphate, trixylenyl phosphate or tricresyl phosphate.
The invention discloses an invention patent with publication number CN109180924A, and relates to a preparation method of a reactive nitrogen-phosphorus flame retardant for waterborne polyurethane, which comprises the following steps: (1) adding 9, 10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide, dicarboxylic acid or anhydride with double bonds and a solvent A into a reaction vessel, uniformly mixing, carrying out addition reaction at 140-180 ℃ for 12-24 h, and carrying out vacuum drying to obtain a phosphorus-containing derivative; (2) adding the phosphorus-containing derivative, diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate, a water-carrying agent B and a catalyst C into a reaction vessel, uniformly mixing, carrying out esterification reaction at 140-160 ℃ for 12-24 h, and carrying out vacuum drying on the reaction mixture to obtain the reactive nitrogen-phosphorus flame retardant.
The invention patent with the publication number of CN103820070A relates to a water-based polyurethane pressure-sensitive adhesive and a preparation method thereof, wherein the pressure-sensitive adhesive consists of the following substances: polyether polyol, flame-retardant modified isocyanate, a compound chain extender and water. Wherein the flame-retardant modified isocyanate is polyol phosphate modified isocyanate, and the compound chain extender is a compound chain extender formed by mixing a polyol chain extender and a sulfonic acid chain extender. The preparation method of the pressure-sensitive adhesive comprises the following steps: (1) mixing the flame retardant and isocyanate for reaction to obtain flame-retardant modified isocyanate; (2) mixing flame-retardant modified isocyanate with polyether polyol, heating for a period of time, and adding one component of a compound chain extender to obtain a prepolymer; (3) adding another component of the compound chain extender into the prepolymer to obtain a polyurethane prepolymer; (4) mixing the polyurethane prepolymer with water to obtain a water-based polyurethane emulsion; (5) the aqueous polyurethane emulsion is applied to a film and dried.
As can be seen from the published relevant documents, no relevant report exists at present for greatly improving flame retardance and avoiding reducing environmental protection indexes of polyurethane foam by using a flame retardant from modified isocyanate.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and the environment-friendly index of the polyurethane foam is reduced by using the physical flame retardant from the modified isocyanate compound. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved.
One of the objects of the present invention is to provide a tris (hydroxymethyl) phosphine oxide-modified isocyanate compound, which is characterized in that: polymerizing trihydroxymethyl phosphine oxide and TDI to obtain a prepolymer, wherein the P content is 4.7%, the N content is 12.7%, the NCO% content is 19%, and the chemical structural formula is as follows:
preferably, the chemical structural formula of the tris (hydroxymethyl) phosphine oxide is as follows:
the second purpose of the invention is to provide a synthetic method of the trihydroxymethyl phosphine oxide modified isocyanate compound, which is characterized by comprising the following steps:
polymerizing the trihydroxymethyl phosphine oxide and TDI to obtain the trihydroxymethyl phosphine oxide modified isocyanate compound, wherein the reaction equation is as follows:
the specific synthesis method comprises the following steps:
1) heating the reaction kettle to 48-52 ℃;
2) according to the following tris (hydroxymethyl) phosphine oxide: adding all TDI with the molar ratio of (4-8) first, and then adding all the tris (hydroxymethyl) phosphine oxide at a constant speed;
3) heating the reaction kettle to 78-82 ℃, and then reacting for 1.9-2.2 h;
4) removing unreacted excessive TDI by using a thin film evaporator;
5) then cooling the reaction kettle to 48-52 ℃, taking out of the kettle and packaging to obtain a product with the P content of 4.7%, the N content of 12.7% and the NCO% content of 19%.
The invention also aims to provide the application of the tris (hydroxymethyl) phosphine oxide modified isocyanate compound in processing polyurethane foam.
The functionality of the trihydroxymethyl phosphine oxide modified isocyanate compound developed by the invention is 3, which is improved by 50 percent compared with the functionality 2, and the produced polyurethane foam product has better compression strength and dimensional stability.
In order to avoid the environmental protection index of polyurethane foam reduced by the flame retardant, the invention solves the problem by starting from the modified isocyanate compound. The modified isocyanate compound provided by the invention can be added with no or little flame retardant in the polyol component, so that the purpose of preventing the flame retardant from reducing the environmental protection index while greatly improving the flame retardance of polyurethane foam is realized. Meanwhile, the modified isocyanate compound developed by the invention does not contain halogen, has small combustion smoke amount, does not release corrosive or irritant hydrogen halide gas, does not generate toxic carcinogenic substances such as polybrominated dioxin and polybrominated dibenzofuran, and does not contain an environmental hormone substance such as a halogen organic substance, thereby avoiding the long-term influence of the material on the environment.
The foam produced by using the modified isocyanate compound developed by the invention is mainly used in the application fields of soft sponge for seats of transportation tools such as mattresses, sofas, automobiles and the like, hard foam for heat preservation of buildings such as refrigeration houses, houses and the like, which need polyurethane foam to have good flame retardant capability and good environmental protection performance such as smell and TVOC. The modified isocyanate compound developed by the invention does not contain halogen, has small combustion smoke quantity, does not release corrosive or irritant hydrogen halide gas, does not generate toxic carcinogenic substances of polybrominated dioxin and polybrominated dibenzofuran, and does not contain an environmental hormone substance of a halogen organic substance, thereby avoiding the long-term influence of materials on the environment.
The modified isocyanate compound may be an aromatic modified isocyanate containing P element obtained by a prepolymerization reaction of tris (hydroxymethyl) phosphine oxide with other aromatic isocyanates MDI, NDI, PPDI, XDI, TXDI, and dimers thereof. Or a prepolymer obtained by polymerization with aliphatic isocyanate such as IPDI (isophorone diisocyanate), HDI (hexamethylene diisocyanate), HMDI, CHDI, TMHDI and the like, and can be used in the fields of foams, coatings, elastomers and the like with yellowing resistance requirements. The modified isocyanate compound developed by the invention does not contain halogen, has small combustion smoke quantity, does not release corrosive or irritant hydrogen halide gas, does not generate toxic carcinogenic substances of polybrominated dioxin and polybrominated dibenzofuran, and does not contain an environmental hormone substance of a halogen organic substance, thereby avoiding the long-term influence of materials on the environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The chemical structure of the tris-hydroxy phosphine oxide-modified isocyanate compound of this example is:
the synthesis method comprises the following steps:
the reference synthesis process comprises the following steps:
(1) heating the reaction kettle to 48-52 ℃;
(2) according to the following tris (hydroxymethyl) phosphine oxide (available from Hubei Xingsheng chemical group Ltd.): adding all TDI with the molar ratio of (4-8) first, and then adding all the tris (hydroxymethyl) phosphine oxide at a constant speed;
(3) heating the reaction kettle to 78-82 ℃, and then reacting for 1.9-2.2 h;
(4) removing unreacted excessive TDI by using a thin film evaporator;
(5) then cooling the reaction kettle to 48-52 ℃, taking out of the kettle and packaging to obtain a product with the P content of 4.7%, the N content of 12.7% and the NCO% content of 19%.
Test examples 1 to 5
The specific examples of the application of the modified isocyanate compound in the test example to polyurethane foam are as follows:
the formulation of the combined polyether polyol is as follows:
| name (R) | Weight percent of |
| F3135 (polyether polyol, Wanhua chemical group Co., Ltd.) | 60 |
| POP3081 (Polymer polyol, Shandong Lanxingdong Co., Ltd.) | 35 |
| Water (W) | 3.5 |
| B8715 Silicone oil (Silicone oil, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.6 |
| A33 (CATALYST, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.3 |
| cat8154 (catalyst, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.5 |
| BL11 (catalyst, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.1 |
| Total of | 100 |
Using 100 parts of the above-mentioned combination polyether polyol and the total parts of the isocyanate component and the physical flame retardant component of each test example in the following table, a foamed article was produced by mixing and stirring.
The isocyanate component and the additive-type flame retardant component of each test example were:
the molar amounts of isocyanate groups (-NCO) in test examples 1, 2 and 3 were equal to each other in accordance with the formulation fractions shown in the above tables, and the molar amount of isocyanate groups (-OH) in 100 parts of the combined polyether polyol was 1.05:1, and a little more than 5% of isocyanate groups ensured sufficient reaction.
The flame retardant and environmental protection performance of each test example is tested as follows:
TVOC test standard: VDA277:1995, odor rating test criteria: VDA270:1992
In the above test examples 1, 2 and 3, the molar number of isocyanate groups (-NCO) in the reaction system was maintained by designing the isocyanate ratio: the ratio of the number of moles of hydroxyl (-OH) groups was 1.05: 1.
Experimental example 2 on the basis of the experimental example 1, the physical flame retardant component TCPP is added, all the other things are unchanged, the oxygen index is increased from 20.2% of non-flame-retardant property to 25.7% of flame-retardant property, but at the same time, the TVOC is increased from 38 mu gC/g to 291 mu gC/g, the odor grade (80 ℃) is increased from 3.5 to 4, and the environmental protection property of the material is seriously influenced while the foam flame-retardant property is increased by the physical flame retardant component TCPP. In the case that the index of the experimental example 3 and the index of the experimental example 1 are kept unchanged (the index is 1.05, namely the ratio of the index to the number of moles of hydroxyl (-OH) of the number of moles of isocyanate (-NCO)), the oxygen index is increased from 20.2% of non-flame-retardant to 26.3% of flame-retardant without adding a physical flame retardant, the TVOC is 38 mu gC/g and 34 mu gC/g respectively, and the odor grade (80 ℃) is 3.5 and 3.5 respectively, so that the change is not large, which shows that the trihydroxymethyl phosphine oxide modified isocyanate compound developed by the invention can realize the purposes of improving the flame retardance of polyurethane foam and avoiding the reduction of the environmental protection index of the flame retardant. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved. Experimental example 3 index and experimental example 2 in the case where the system index was maintained (index of 1.05), experimental examples 3 and 2 improved the foam flame retardance to an oxygen index comparable by modifying the isocyanate compound with trimethylol phosphine oxide and adding the physical flame retardant component TCPP, respectively, but the TVOCs of experimental examples 3 and 2 were 34 μ g c/g and 291 μ g c/g, respectively, and the odor grades (80 ℃) were 3.5 and 4, respectively. In particular, TVOC is changed by orders of magnitude, which shows that the use of the tris (hydroxymethyl) phosphine oxide modified isocyanate compound for improving flame retardance has obvious advantages in environmental protection compared with the use of a physical flame retardant component TCPP.
In each of the above test examples 3, 4 and 5, 114 parts of isocyanate was used by keeping the amount of isocyanate constant.
Experimental example 5 on the basis of the experimental example 4, the physical flame retardant component TCPP is added, all the other things are unchanged, the oxygen index is increased from 20.5% of non-flame-retardant property to 26.1% of flame-retardant property, but at the same time, the TVOC is increased from 31 mu gC/g to 343 mu gC/g, the odor grade (80 ℃) is increased from 3.5 to 4, and the environmental protection property of the material is seriously influenced while the flame-retardant property of the foam is increased by the physical flame retardant component TCPP. Under the condition that the indexes of example 3 and example 4 are 114 parts of cyanate ester, the oxygen index is increased from 20.5% of non-flame-retardant to 26.3% of flame-retardant without adding a physical flame retardant, the TVOC is 34 mu gC/g and 31 mu gC/g respectively, and the odor grade (80 ℃) is 3.5 and 3.5 respectively, so that the change is not large, and the purpose of simultaneously improving the flame retardance of polyurethane foam and avoiding the reduction of environmental protection indexes by the flame retardant can be realized by the trihydroxymethyl phosphine oxide modified isocyanate compound developed by the invention. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved. Experimental example 3 index and experimental example 5 in the case where the amount of isocyanate was maintained to be 114 parts, experimental examples 3 and 5 improved the foam flame retardance to an oxygen index comparable by modifying the isocyanate compound with trimethylol phosphine oxide and adding the physical flame retardant component TCPP, respectively, but the TVOCs of experimental examples 3 and 5 were 34 μ g c/g, 343 μ g c/g, respectively, and the odor grades (80 ℃) were 3.5, 4, respectively. Particularly, the TVOC is changed by orders of magnitude, which shows that the flame retardance is improved by using the trihydroxymethyl phosphine oxide modified isocyanate compound, and the TVOC has obvious advantages in environmental protection compared with the physical flame retardant component TCPP.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (5)
1. The trihydroxymethyl phosphine oxide modified isocyanate compound is characterized in that: polymerizing trihydroxymethyl phosphine oxide and TDI to obtain a prepolymer, wherein the P content is 4.7%, the N content is 12.7%, the NCO% content is 19%, and the chemical structural formula is as follows:
2. the tris-hydroxy phosphine oxide-modified isocyanate compound according to claim 1, wherein the tris-hydroxy phosphine oxide has the following chemical structural formula:
3. the method for synthesizing a tris (hydroxymethyl) phosphine oxide-modified isocyanate compound according to any one of claims 1 to 2, characterized by comprising the steps of:
polymerizing the trihydroxymethyl phosphine oxide and TDI to obtain the trihydroxymethyl phosphine oxide modified isocyanate compound, wherein the reaction equation is as follows:
4. the method for synthesizing the tris (hydroxymethyl) phosphine oxide-modified isocyanate compound according to claim 3, characterized in that the specific synthesis method is as follows:
1) heating the reaction kettle to 48-52 ℃;
2) according to the following tris (hydroxymethyl) phosphine oxide: adding all TDI with the molar ratio of (4-8) first, and then adding all the tris (hydroxymethyl) phosphine oxide at a constant speed;
3) heating the reaction kettle to 78-82 ℃, and then reacting for 1.9-2.2 h;
4) removing unreacted excessive TDI by using a thin film evaporator;
5) then cooling the reaction kettle to 48-52 ℃, taking out of the kettle and packaging to obtain a product with the P content of 4.7%, the N content of 12.7% and the NCO% content of 19%.
5. Use of the trishydroxymethylphosphine oxide-modified isocyanate compound according to claim 1 for processing polyurethane foam.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805742A (en) * | 2022-05-31 | 2022-07-29 | 中国科学技术大学 | Preparation method of degradable high-strength polyurethane elastomer |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
| CN116082736A (en) * | 2023-02-13 | 2023-05-09 | 重庆日鑫包装制品有限公司 | High-toughness environment-friendly pearl cotton section bar for packaging and preparation method thereof |
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| CN102050836A (en) * | 2010-12-20 | 2011-05-11 | 武汉金磷化工科技有限责任公司 | Phosphorus-containing polyisocyanate and preparation method thereof |
| CN110483578A (en) * | 2019-08-29 | 2019-11-22 | 北京理工大学 | A kind of response type phosphor nitrogen combustion inhibitor and preparation method thereof |
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| US3758554A (en) * | 1971-06-18 | 1973-09-11 | Stevens & Co Inc J P | Phosphorus-containing carbamates |
| SU572465A1 (en) * | 1973-03-19 | 1977-09-15 | Казанский Химико-Технологический Институт Имени С.М.Кирова | Method of preparing tris-(toluilen-2-izocianato-4-carbamoiloxymethyl) of phosphine or its oxide |
| CN102050836A (en) * | 2010-12-20 | 2011-05-11 | 武汉金磷化工科技有限责任公司 | Phosphorus-containing polyisocyanate and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805742A (en) * | 2022-05-31 | 2022-07-29 | 中国科学技术大学 | Preparation method of degradable high-strength polyurethane elastomer |
| CN114805742B (en) * | 2022-05-31 | 2023-12-12 | 中国科学技术大学 | Preparation method of degradable high-strength polyurethane elastomer |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
| CN116082736A (en) * | 2023-02-13 | 2023-05-09 | 重庆日鑫包装制品有限公司 | High-toughness environment-friendly pearl cotton section bar for packaging and preparation method thereof |
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