CN116554435A - High-functionality modified flame-retardant isocyanate compound and synthesis method thereof - Google Patents
High-functionality modified flame-retardant isocyanate compound and synthesis method thereof Download PDFInfo
- Publication number
- CN116554435A CN116554435A CN202210108754.3A CN202210108754A CN116554435A CN 116554435 A CN116554435 A CN 116554435A CN 202210108754 A CN202210108754 A CN 202210108754A CN 116554435 A CN116554435 A CN 116554435A
- Authority
- CN
- China
- Prior art keywords
- isocyanate compound
- flame
- modified flame
- retardant
- flame retardant
- 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
- 239000012948 isocyanate Substances 0.000 title claims abstract description 64
- -1 modified flame-retardant isocyanate compound Chemical class 0.000 title claims abstract description 44
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 19
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- AZUXKVXMJOIAOF-UHFFFAOYSA-N 1-(2-hydroxypropoxy)propan-2-ol Chemical compound CC(O)COCC(C)O AZUXKVXMJOIAOF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 8
- LCLPYJSGWJTDPD-UHFFFAOYSA-N phosphorous acid;propane-1,2-diol Chemical compound OP(O)O.CC(O)CO.CC(O)CO LCLPYJSGWJTDPD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 230000007613 environmental effect Effects 0.000 abstract description 23
- 239000006260 foam Substances 0.000 abstract description 14
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 229910052736 halogen Inorganic materials 0.000 abstract description 12
- 150000002367 halogens Chemical class 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- HPARLNRMYDSBNO-UHFFFAOYSA-N 1,4-benzodioxine Chemical class C1=CC=C2OC=COC2=C1 HPARLNRMYDSBNO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000711 cancerogenic effect Effects 0.000 abstract description 4
- 231100000315 carcinogenic Toxicity 0.000 abstract description 4
- 150000004826 dibenzofurans Chemical class 0.000 abstract description 4
- 239000005556 hormone Substances 0.000 abstract description 4
- 229940088597 hormone Drugs 0.000 abstract description 4
- 239000012433 hydrogen halide Substances 0.000 abstract description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 239000002085 irritant Substances 0.000 abstract description 3
- 231100000021 irritant Toxicity 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 description 57
- 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 54
- 150000002513 isocyanates Chemical class 0.000 description 27
- 238000012360 testing method Methods 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 238000002360 preparation method Methods 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
- 238000002156 mixing Methods 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
- 239000000839 emulsion Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000000576 coating method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YFHCUNVROJHJHV-UHFFFAOYSA-N BrC=1C=C(C=C(C=1)N=C=O)N=C=O Chemical group 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 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
- 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
- 238000003756 stirring Methods 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
- 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
- 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 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 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
- 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
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 125000006267 biphenyl group Chemical group 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 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
- 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000003472 neutralizing effect 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
- VXZJUYUVOQZBNU-UHFFFAOYSA-N phosphoric acid 1,2-xylene Chemical compound P(=O)(O)(O)O.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C VXZJUYUVOQZBNU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002265 prevention Effects 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
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 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
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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
The invention relates to a high-functionality modified flame-retardant isocyanate compound and a synthesis method thereof, belonging to the technical field of polyurethane materials. The invention uses tri (di-1, 2-propylene glycol) phosphite ester and TDI to polymerize to obtain a high-functionality modified flame-retardant isocyanate compound. The modified flame-retardant isocyanate compound containing the P element does not contain halogen, and can greatly improve the flame retardance of the polyurethane foam and simultaneously does not reduce the environmental protection index of the foam. The modified flame-retardant 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 cancerogenic substances namely polybrominated benzo-dioxin and polybrominated dibenzofuran, does not contain environmental hormone substances such as halogen organic substances, and avoids the long-term influence of materials on the environment.
Description
Technical Field
The invention relates to a high-functionality modified flame-retardant isocyanate compound and a synthesis method thereof, belonging to the technical field of polyurethane materials.
Background
The total annual production of polyurethane is about 2000 ten thousand tons, the production of China is about 55% of the world production, and the most widely applied and most used product is foam product which accounts for about 40% of the share. The largest amount of polyurethane foam products is soft sponge for seats of vehicles such as mattresses, sofas and automobiles, and rigid foam for heat preservation of buildings such as refrigerators, cold houses and houses, and the polyurethane foam has good flame retardant capability and good environmental protection performance such as smell and TVOC.
On the one hand, flame retardance has become a neck problem of polyurethane foam used in the fields of refrigerators, buses, trains, public houses and the like. Polyurethane foam as a foam is flammable by itself if no flame retardant is added. The combustion characteristic of the GB38262-2019 passenger car interior material is carried out on the 7 th month and 1 st 2020, and the horizontal combustion of the polyurethane seat is regulated to be A0 level, and the vertical combustion is less than or equal to 100mm/min; the polyurethane heat-insulating noise-reducing material needs to meet the oxygen index of 25% and 28% besides horizontal/vertical combustion. In the train field: gao Tiehe general seats have flame retardant performance oxygen indexes respectively reaching 28% (the technical condition of flame retardant materials for built-in motor train units of TBT 3237-2010) and 26% (the technical condition of flame retardant materials for locomotives of TBT 3138-2006), and greatly improve the industry admission threshold.
The polyurethane foam is formed by the reaction of isocyanate and polyol, and the current research for improving the flame retardance of polyurethane foam is mostly focused on the polyol component, and mainly comprises the following steps:
1. the phosphorus or halogen liquid flame retardant is added into the polyol component, so that the problems of strong plasticizing effect, flame retardant migration and the like exist;
2. the polyol with flame retardant elements such as phosphorus, nitrogen, halogen and the like is developed, and the problems of poor physical properties, unsatisfactory flame retardant effect and high cost exist;
3. the solid flame retardant such as expandable graphite, aluminum hydroxide and the like is added to realize flame retardance, and the product and the process face are narrower.
The halogen flame retardant has large smoke quantity, the released hydrogen halide has corrosiveness or irritation, and can generate toxic cancerogenic substances namely polybrominated benzodioxin and polybrominated dibenzofuran, most of halogen organic substances are environmental hormone substances, and can induce organism mutation to influence the immune system, endocrine system and reproductive system of a human body and influence the normal metabolism of the human body. The RoHS directive, beginning at 7 and 1 in the european union, strictly limits the use of polybrominated diphenyl ether, PBDE, polybrominated diphenyl, PBB, and the requirement for prohibiting the use of halogen flame retardants in electronic display housings and brackets was issued at 12 and 5 in 2019.
On the other hand, the environmental protection problems such as TVOC and smell are another neck clamping problem of the application of polyurethane flame-retardant foam in closed spaces such as vehicles. For example, china business report 2018.6.23 reports that "Fuxing number frequently suffers from in-car odor complaints, the total of middle-grade iron: and (5) carrying out self-checking and strictly controlling raw material purchase. Flame retardance and environmental protection are mutually opposite indexes, and flame retardant is one of the factors contributing to TVOC and smell the most.
The difficulty with the problem is that high flame retardance and low TVOC low odor are two mutually contradictory indicators, as the physically added flame retardant is one of the factors that contribute most to TVOC and odor of flame retardant flexible foam.
The modified isocyanate patents related to flame retardance are: the invention patent with publication number of CN105949435A relates to a self-flame-retardant aqueous 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 groups, 2-10 parts of small molecule chain extender, 0.02-0.1 part of dibutyltin dilaurate, 2-5 parts of neutralizer triethylamine, 1-3 parts of organic amine chain extender and 80-150 parts of deionized water. The preparation method is also provided: firstly, stirring, nitrogen protection, heating, adding a diluent, a small molecular chain extender, dibutyl tin dilaurate and the like to prepare a modified polyurethane prepolymer, neutralizing, emulsifying and aqueous phase chain extension of the modified polyurethane prepolymer, and finally, distilling the solvent under reduced pressure to obtain the self-flame-retardant aqueous polyurethane emulsion.
The invention patent application with publication number of CN109970605A provides bromine-containing diisocyanate with flame retardant property, and the structure name is 1-bromo-3, 5-diisocyanatobenzene, which can be used as a flame retardant for polyurea coating. The preparation method comprises the following steps: (1) 5-bromo-isophthalic acid in SOCl 2 Reflux reaction, then evaporating SOCl under reduced pressure 2 Obtaining 5-bromo-m-phthaloyl chloride; (2) 5-bromo-isophthaloyl dichloride was dissolved in THF and NaN was then added 3 Adding saturated NaHCO into the mixed solution 3 Extracting with toluene, drying the organic layer and evaporating under reduced pressure to obtain a toluene solution of 5-bromo-m-dibenzoyl diazide; (3) Refluxing the toluene solution of 5-bromo-m-dibenzoyl diazide to remove toluene and obtain 1-bromo-3, 5-diisocyanatobenzene.
The invention of publication number CN112041364a relates to two-component adhesive compositions useful for food packaging, pharmaceutical packaging and industrial lamination. The adhesive composition includes (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., premixing 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 of CN112375207A provides phosphorus-nitrogen modified isocyanate which can be directly used as a raw material to participate in the synthesis of polyurethane materials, 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 200-220 parts of solvent, and heating and stirring to obtain silicon phosphate; (2) 100-180 parts of unsaturated isocyanate, 0.31-0.73 part of chloroplatinic acid and 2.5-4.5 parts of 1,1' -bis (dimethylsilyl) ferrocene are added into the silicon phosphate, and after the reaction, the solvent is distilled off, so that the phosphorus-nitrogen modified isocyanate can be obtained.
The invention patent with publication number of CN110184016A discloses a flame-retardant two-component polyurethane adhesive for a new energy battery, which comprises A, B two components, wherein the component A comprises: 55-85% of modified isocyanate prepolymer, 6-20% of flame retardant a, 8-22% of filler a and 1-3% of stabilizer; composition of B: 30-75% of polyol, 3-10% of amine, 2-5% of coupling agent, 10-30% of flame retardant b and 10-25% of filler b. 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 hydroxyl-containing phosphorus flame retardant, 0.05-1 part of dibutyl tin dilaurate and 0.05-5 parts of polymerization inhibitor; flame retardant a and flame retardant b are independently selected from one of toluene diphenyl phosphate, isopropylated triphenyl phosphate, tri (xylene) phosphate or tricresyl phosphate.
The invention patent with publication number of CN109180924A 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 container, uniformly mixing, carrying out esterification reaction at 140-160 ℃ for 12-24 h, and then vacuum drying the mixture obtained by the reaction to obtain the reactive nitrogen-phosphorus flame retardant.
The invention patent with 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 obtained by mixing a polyol chain extender and a sulfonic acid type chain extender. The preparation method of the pressure-sensitive adhesive comprises the following steps: (1) The flame retardant is mixed with isocyanate for reaction to obtain flame-retardant modified isocyanate; (2) Mixing flame-retardant modified isocyanate and 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 polyurethane prepolymer with water to obtain aqueous polyurethane emulsion; (5) coating the aqueous polyurethane emulsion on the film and drying.
From the above-mentioned published related documents, there is no report on the prevention of the flame retardant from decreasing the environmental protection index of polyurethane foam while greatly improving the flame retardant property from the modified isocyanate.
Disclosure of Invention
The invention aims to solve the defects existing in the prior art, and the modified flame-retardant isocyanate compound prevents the physical flame retardant from reducing the environmental protection index of the polyurethane foam, and the high-functionality modified flame-retardant isocyanate compound can not add or add little flame retardant into the polyol component, so that the aims of simultaneously improving the flame retardance of the polyurethane foam and simultaneously avoiding the flame retardant from reducing the environmental protection index are fulfilled. Solves the problem that environmental protection indexes such as high flame retardance, low TVOC, low odor and the like are mutually opposite.
The invention aims at providing a high-functionality modified flame-retardant isocyanate compound, which is characterized in that: the prepolymer is polymerized by tris (di-1, 2-propanediol) phosphite ester and TDI, the P content of the prepolymer is 3.3 percent, the N content of the prepolymer is 8.8 percent, the NCO content of the prepolymer is 13.2 percent, and the chemical structural formula of the prepolymer is as follows:
preferably, the tris (di-1, 2-propanediol) phosphite has the chemical formula:
the invention also provides a synthesis method of the high-functionality modified flame-retardant isocyanate compound, which is characterized by comprising the following steps of:
the tri (di-1, 2-propylene glycol) phosphite ester and TDI are polymerized to obtain the high-functionality modified flame-retardant isocyanate compound, and the reaction equation is as follows:
the specific synthesis method is as follows:
1) Heating the reaction kettle to 48-52 ℃;
2) Tris (di-1, 2-propanediol) phosphite in molar ratio: TDI=1 (4-8), all TDI is added first, and then all tris (1, 2-propanediol) phosphite is added at 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 a thin film evaporator;
5) And then cooling the reaction kettle to 48-52 ℃, and taking out of the kettle for packaging to obtain a product with the P content of 3.3%, the N content of 8.8% and the NCO content of 13.2%.
The invention further aims to provide an application of the high-functionality modified flame-retardant isocyanate compound in processing polyurethane foam.
The functionality of the high-functionality modified flame-retardant isocyanate compound developed by the invention is 3, and compared with the functionality of TDI (toluene diisocyanate) which is improved by 50%, the polyurethane foam product produced by the invention has better compressive strength and dimensional stability.
In order to avoid the flame retardant from reducing the environmental protection index of the polyurethane foam, the invention solves the problem from the modified flame-retardant isocyanate compound, and the modified flame-retardant isocyanate compound can not be added or be added with little flame retardant in the polyol component, thereby realizing the purposes of greatly improving the flame retardance of the polyurethane foam and simultaneously avoiding the flame retardant from reducing the environmental protection index. Meanwhile, the modified flame-retardant 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 cancerogenic substances namely polybrominated benzo-dioxin and polybrominated dibenzofuran, does not contain environmental hormone substances such as halogen organic substances, and avoids the long-term influence of materials on the environment.
The foam produced by using the modified flame-retardant isocyanate compound developed by the invention is mainly used in a plurality of application fields such as soft sponge for vehicle seats of mattresses, sofas, automobiles and the like, rigid foam for heat preservation of buildings of refrigerators, houses and the like, which need polyurethane foam to have good flame-retardant capability and also have good environmental protection performances such as odor, TVOC and the like. The modified flame-retardant 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 cancerogenic substances namely polybrominated benzo-dioxin and polybrominated dibenzofuran, does not contain environmental hormone substances such as halogen organic substances, and avoids the long-term influence of materials on the environment.
The modified flame-retardant isocyanate compound of the invention can also be aromatic modified isocyanate containing P element, which is obtained by the prepolymerization reaction of tris (di-1, 2-propanediol) phosphite ester, other aromatic isocyanate MDI, NDI, PPDI, XDI, TXDI, dimers thereof and the like. Or a prepolymer obtained by polymerizing with an 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.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The chemical structural formula of the high-functionality modified flame-retardant isocyanate compound is as follows:
the synthesis method comprises the following steps:
the reference synthesis process is as follows:
(1) Heating the reaction kettle to 48-52 ℃;
(2) Tris (di-1, 2-propanediol) phosphite (available from Qingdao Union beautification Co., ltd.) in molar ratio: TDI=1 (4-8), all TDI is added first, and then all tris (1, 2-propanediol) phosphite is added at 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 a thin film evaporator;
(5) And then cooling the reaction kettle to 48-52 ℃, and taking out of the kettle for packaging to obtain a product with the P content of 3.3%, the N content of 8.8% and the NCO content of 13.2%.
Test examples
The application of the modified isocyanate compound of this test example to polyurethane foam is as follows:
the formulation of the combined polyether polyol is as follows:
using 100 parts of the above-mentioned polyether polyol, 100 parts of the above-mentioned polyether polyol was mixed with the total parts of the isocyanate component and the physical flame retardant component of each test example in the following table, and stirred, to prepare a foam article.
The isocyanate component and the additive flame retardant component of each test example were:
the above test examples 1,2 and 3 were equal in terms of the number of moles of isocyanate groups (-NCO) corresponding to the formulation fractions of the above tables, and the ratio of the number of moles of hydroxyl groups (-OH) to the number of moles of isocyanate groups (-OH) contained in 100 parts of the combined polyether polyol was 1.05:1, and a small amount of isocyanate groups 5% more ensured that the reaction was sufficiently carried out.
The flame retardant and environment-friendly performance of each test example is tested as follows:
TVOC test standard: VDA277:1995, odor rating test Standard: 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 molar ratio of hydroxyl groups (-OH) was 1.05:1.
Test example 2 the addition of the physical flame retardant component TCPP on the basis of example 1, everything else being unchanged, the oxygen index increased from 20.2% without flame retardance to 25.0% with flame retardance, but at the same time the TVOC increased from 38 μg c/g to 179 μg c/g and the odor grade (80 ℃) increased from 3.5 to 4, it was seen that the physical flame retardant component TCPP severely affected the environmental performance of the material while increasing the flame retardance of the foam.
Test example 3 and example 1, with the system index unchanged (the index is 1.05, that is, the ratio of the moles of isocyanate (-NCO) to the moles of hydroxyl (-OH), without adding a physical flame retardant, the oxygen index is increased from 20.2% of flame retardance to 25.2% of flame retardance, and TVOC is 38 μg C/g and 29 μg C/g, respectively, and the odor grades (80 ℃) are 3.5 and 3.5, respectively, show that the high-functionality modified flame retardant isocyanate compound developed by the invention can achieve the purposes of simultaneously improving the flame retardance of polyurethane foam and avoiding the flame retardant from reducing the environmental protection index. Solves the problem that environmental protection indexes such as high flame retardance, low TVOC, low odor and the like are mutually opposite.
Test example 3 the index and example 2 with the system index unchanged (index 1.05), examples 3 and 2 improved foam flame retardance to oxygen index by the addition of the physical flame retardant component TCPP, respectively, using the high functionality modified flame retardant isocyanate compound, but TVOC of examples 3 and 2 were 29 μg c/g, 179 μg c/g, respectively, and odor rating (80 ℃) was 3.5, 4, respectively. In particular, TVOC has changed about 6 times, indicating that the use of a high functionality modified flame retardant isocyanate compound to increase flame retardance has a significant advantage over the use of a physical flame retardant component TCPP in environmental protection.
In each of the above test examples 3, 4 and 5, 165 parts by keeping the amount of isocyanate constant.
Test example 5 the addition of the physical flame retardant component TCPP on the basis of test example 4, everything else being unchanged, the oxygen index increased from 20.8% without flame retardance to 25.6% without flame retardance, but at the same time the TVOC increased from 27 μg c/g to 329 μg c/g and the odor grade (80 ℃) increased from 3.5 to 4, it was seen that the physical flame retardant component TCPP severely affected the environmental performance of the material while increasing the flame retardance of the foam.
Under the condition that the indexes of test example 3 and test example 4 keep the amount of cyanate to be 165 parts, no physical flame retardant is added, the oxygen index is increased from 20.8% of flame retardance to 25.2% of flame retardance, meanwhile, TVOC is respectively 29 mu gC/g and 27 mu gC/g, and the odor grades (80 ℃) are respectively 3.5 and 3.5, which shows that the high-functionality modified flame retardant isocyanate compound developed by the invention can realize the purposes of simultaneously improving the flame retardance of polyurethane foam and simultaneously avoiding the flame retardant from reducing the environmental protection index. Solves the problem that environmental protection indexes such as high flame retardance, low TVOC, low odor and the like are mutually opposite.
Test example 3 the amount of isocyanate was kept unchanged at 165 parts for test example 3 and test example 5, and the flame retardance of the foam was improved to a small difference in oxygen index by using a high-functionality modified flame retardant isocyanate compound and adding a physical flame retardant component TCPP, respectively, but TVOC of test examples 3 and 5 was 29. Mu.gC/g, 328. Mu.gC/g, and odor grade (80 ℃) was 3.5, 4.0, respectively. TVOC changes by orders of magnitude, indicating that the use of high functionality modified flame retardant isocyanate compounds to increase flame retardance provides significant environmental advantages over the use of the physical flame retardant component TCPP.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. While the foregoing describes the embodiments of the present invention, it should be understood that the present invention is not limited to the embodiments, and that various modifications and changes can be made by those skilled in the art without any inventive effort.
Claims (6)
1. A high functionality modified flame retardant isocyanate compound characterized by: the prepolymer is polymerized by tris (di-1, 2-propanediol) phosphite ester and TDI, the P content of the prepolymer is 3.3 percent, the N content of the prepolymer is 8.8 percent, the NCO content of the prepolymer is 13.2 percent, and the chemical structural formula of the prepolymer is as follows:
2. a high functionality modified flame retardant isocyanate compound according to claim 1, wherein said tris (di-1, 2-propanediol) phosphite has the chemical formula:
3. a high-functionality modified flame retardant isocyanate compound according to claim 1, wherein said high-functionality modified flame retardant isocyanate compound has a functionality of 3.
4. A method for synthesizing a high-functionality modified flame retardant isocyanate compound according to any one of claims 1 to 3, comprising the steps of:
the tri (di-1, 2-propylene glycol) phosphite ester and TDI are polymerized to obtain the high-functionality modified flame-retardant isocyanate compound, and the reaction equation is as follows:
5. the method for synthesizing a high-functionality modified flame-retardant isocyanate compound according to claim 4, wherein the specific synthesis method is as follows:
1) Heating the reaction kettle to 48-52 ℃;
2) Tris (di-1, 2-propanediol) phosphite in molar ratio: TDI=1 (4-8), all TDI is added first, and then all tris (1, 2-propanediol) phosphite is added at 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 a thin film evaporator;
5) And then cooling the reaction kettle to 48-52 ℃, and taking out of the kettle for packaging to obtain a product with the P content of 3.3%, the N content of 8.8% and the NCO content of 13.2%.
6. Use of a high-functionality modified flame-retardant isocyanate compound according to claim 1 for processing polyurethane foams.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108754.3A CN116554435A (en) | 2022-01-28 | 2022-01-28 | High-functionality modified flame-retardant isocyanate compound and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108754.3A CN116554435A (en) | 2022-01-28 | 2022-01-28 | High-functionality modified flame-retardant isocyanate compound and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116554435A true CN116554435A (en) | 2023-08-08 |
Family
ID=87498764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210108754.3A Pending CN116554435A (en) | 2022-01-28 | 2022-01-28 | High-functionality modified flame-retardant isocyanate compound and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554435A (en) |
-
2022
- 2022-01-28 CN CN202210108754.3A patent/CN116554435A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3707777B2 (en) | Polyether polyurethane | |
| CN114478626B (en) | Difunctional modified flame-retardant isocyanate compound and synthesis method thereof | |
| CN114409863A (en) | Trihydroxymethyl phosphine oxide modified isocyanate compound and synthesis method thereof | |
| CN105849151B (en) | Polyalcohol and corresponding polyurethane based on dimer fatty acid residue | |
| JP6942139B2 (en) | Reactive flame retardants for polyurethane foams and polyisocyanurate foams | |
| JPH0229417A (en) | Liquid polyisocyanate composition, production thereof and use thereof for producing soft polyurethane foam | |
| JP2011529997A (en) | Aromatic polyester, polyol blend containing the same, and product obtained therefrom | |
| CN101104149B (en) | Stabilized carbanions as trimerization catalysts | |
| CA2119827C (en) | Two-component aqueous polyurethane dispersions having improved pot life and coatings prepared therefrom | |
| KR20090057413A (en) | Polyamide resin containing terminal isocyanate group, alkoxysilane-modified polyamide resin, processes for production of the resins, hot-melt adhesive agent, and cured resin product | |
| KR102099755B1 (en) | Process for producing polymer foams comprising imide groups | |
| JP2013245312A (en) | Composition for adhesive | |
| JP5071958B2 (en) | Aqueous polyurethane composition | |
| WO2007007577A1 (en) | Composition for forming water-expanded rigid polyisocyanurate foam, process for producing water-expanded rigid polyisocyanurate foam from the composition, and water-expanded rigid polyisocyanurate foam obtained by the process | |
| US11840598B2 (en) | Urethane resin | |
| TWI752047B (en) | Polycarbodiimide composition, method for producing polycarbodiimide composition, water-dispersed composition, solution composition, resin composition, and resin cured product | |
| CN114437127B (en) | Phosphine oxide derivative-based modified isocyanate compound and synthesis method thereof | |
| CN116554435A (en) | High-functionality modified flame-retardant isocyanate compound and synthesis method thereof | |
| JP6138325B1 (en) | Polyurethane resin composition | |
| CN112739737B (en) | Polyurethane with improved hardness | |
| JP2020180170A (en) | Halogen-containing polyether polyol composition | |
| JP2012529542A (en) | Method for producing polyester polyol with low amount of dioxane waste | |
| JP5356096B2 (en) | Modified polytetramethylene ether glycol, process for producing the same, and polyurethane resin | |
| JPH02135212A (en) | Polyurethane composition | |
| WO2018139553A1 (en) | Halogen-containing polyether polyol and polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |