US20020061936A1 - Foamed isocyanate-based polymer having improved hardness properties and process for production thereof - Google Patents
Foamed isocyanate-based polymer having improved hardness properties and process for production thereof Download PDFInfo
- Publication number
- US20020061936A1 US20020061936A1 US09/917,235 US91723501A US2002061936A1 US 20020061936 A1 US20020061936 A1 US 20020061936A1 US 91723501 A US91723501 A US 91723501A US 2002061936 A1 US2002061936 A1 US 2002061936A1
- Authority
- US
- United States
- Prior art keywords
- process defined
- active hydrogen
- isocyanate
- macromolecule
- diisocyanate
- 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.)
- Abandoned
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 121
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 89
- 229920000642 polymer Polymers 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 102
- 229920005862 polyol Polymers 0.000 claims abstract description 101
- 229920002521 macromolecule Polymers 0.000 claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- 239000001257 hydrogen Substances 0.000 claims abstract description 55
- 239000006260 foam Substances 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 239000011541 reaction mixture Substances 0.000 claims abstract description 32
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 43
- -1 fatty acid triglycerides Chemical class 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000001413 cellular effect Effects 0.000 claims description 14
- 229920000768 polyamine Polymers 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000007373 indentation Methods 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 6
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 5
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 4
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical class O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 claims description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- FWWWRCRHNMOYQY-UHFFFAOYSA-N 1,5-diisocyanato-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(N=C=O)C=C1N=C=O FWWWRCRHNMOYQY-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical class ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 claims description 2
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 claims description 2
- DTZHXCBUWSTOPO-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylphenyl)methyl]-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(CC=2C=C(C)C(N=C=O)=CC=2)=C1 DTZHXCBUWSTOPO-UHFFFAOYSA-N 0.000 claims description 2
- VOUDXMXYROJCKN-UHFFFAOYSA-N 2,4-diisocyanato-1,3,5-triazine Chemical compound O=C=NC1=NC=NC(N=C=O)=N1 VOUDXMXYROJCKN-UHFFFAOYSA-N 0.000 claims description 2
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- FZWBABZIGXEXES-UHFFFAOYSA-N ethane-1,2-diol;hexanedioic acid Chemical compound OCCO.OC(=O)CCCCC(O)=O FZWBABZIGXEXES-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000004072 triols Chemical class 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims 4
- 125000001033 ether group Chemical group 0.000 claims 4
- 239000004970 Chain extender Substances 0.000 claims 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims 1
- 150000001408 amides Chemical group 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- 229920002396 Polyurea Polymers 0.000 description 15
- 229920002635 polyurethane Polymers 0.000 description 13
- 239000004814 polyurethane Substances 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000582 polyisocyanurate Polymers 0.000 description 8
- 229920005830 Polyurethane Foam Polymers 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000011496 polyurethane foam Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011495 polyisocyanurate Substances 0.000 description 6
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920000638 styrene acrylonitrile Polymers 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000412 dendrimer Substances 0.000 description 5
- 229920000736 dendritic polymer Polymers 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- JVPNULGQLDLIRJ-UHFFFAOYSA-N 1-diisocyanatophosphorylethane Chemical compound O=C=NP(=O)(CC)N=C=O JVPNULGQLDLIRJ-UHFFFAOYSA-N 0.000 description 1
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- CBJMLVAWVCHUBA-UHFFFAOYSA-N diisocyanatophosphorylbenzene Chemical compound O=C=NP(=O)(N=C=O)C1=CC=CC=C1 CBJMLVAWVCHUBA-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 210000004124 hock Anatomy 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000003643 water by type Substances 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Definitions
- the present invention relates to a foamed isocyanate-based polymer having improved hardness properties.
- the present invention relates to a process for the production of such a foamed isocyanate-based polymer.
- the present invention relates to a method for improving the hardness characteristics of an isocyanate-based foam.
- the present invention relates to a dispersion of a dendritic macromolecule and an active hydrogen-containing compound useful in the production of foamed isocyanate-based polymer.
- Isocyanate-based polymers are known in the art. Generally, those of skill in the art understand isocyanate-based polymers to be polyurethanes, polyureas, polyisocyanurates and mixtures thereof.
- One of the conventional ways to produce a polyurethane foam is known as the “one-shot” technique.
- the isocyanate, a suitable polyol, a catalyst, water (which acts as a reactive “blowing” agent and can optionally be supplemented with one or more physical blowing agents) and other additives are mixed together at once using, for example, impingement mixing (e.g., high pressure).
- impingement mixing e.g., high pressure
- the polyol would be replaced with a suitable polyamine.
- a polyisocyanurate may result from cyclotrimerization of the isocyanate component.
- Urethane modified polyureas or polyisocyanurates are known in the art. In either scenario, the reactants would be intimately mixed very quickly using a suitable mixing technique.
- prepolymer Another technique for producing foamed isocyanate-based polymers is known as the “prepolymer” technique.
- a prepolymer is produced by reacting polyol and isocyanate (in the case of a polyurethane) in an inert atmosphere to form a liquid polymer terminated with reactive groups (e.g., isocyanate moieties and active hydrogen moieties).
- the prepolymer is thoroughly mixed with a lower molecular weight polyol (in the case of producing a polyurethane) or a polyamine (in the case of producing a modified polyurea) in the presence of a curing agent and other additives, as needed.
- filler materials have been introduced into foamed polymers by loading the filler material into one or both of the liquid isocyanate and the liquid active hydrogen-containing compound (i.e., the polyol in the case of polyurethane, the polyamine in the case of polyurea, etc.).
- the filler material serves the purpose of conferring so-called loaded building properties to the resulting foam product.
- filler materials used in the reaction mixture can vary, to a certain extent, depending on the desired physical properties of the foamed polymer product, and limitations imposed by mixing techniques, the stability of the system and equipment imposed limitations (e.g., due to the particle size of the filler material being incompatible with narrow passages, orifices and the like of the equipment).
- graft copolymer polyols are polyols, preferably polyether polyols, which contain other organic polymers. It is known that such graft copolymer polyols are useful to confer hardness (i.e., load building) to the resultant polyurethane foam compared to the use of polyols which have not been modified by incorporating the organic polymers.
- graft copolymer polyols there are two main categories which may be discussed: (i) chain-growth copolymer polyols, and (ii) step-growth copolymer polyols.
- Chain-growth copolymer polyols generally are prepared by free radical polymerization of monomers in a polyol carrier to produce a free radical polymer dispersed in the polyol carrier.
- the free radical polymer can be based on acrylonitrile or styrene-acrylonitrile (SAN).
- the solids content of the polyol is typically up to about 60%, usually in the range of from about 15% to about 40%, by weight of the total weight of the composition (i.e., free radical polymer and polyol carrier).
- these chain-growth copolymer polyols have a viscosity in the range of from about 2,000 to about 8,000 centipoise. When producing such chain-growth copolymer polyols, it is known to induce grafting of the polyol chains to the free-radical polymer.
- Step-growth copolymer polyols generally are characterized as follows: (i) PHD (Polyharnstoff Disperion) polyols, (ii) PIPA (Poly Isocyanate Poly Addition) polyols, and (iii) epoxy dispersion polyols.
- PHD polyols are dispersions of polyurea particles in conventional polyols and generally are formed by the reaction of a diamine (e.g., hydrazine) with a diisocyanate (e.g., toluene diisocyanate) in the presence of a polyether polyol.
- the solids content of the PHD polyols is typically up to about 50%, usually in the range of from about 15% to about 40%, by weight of the total weight of the composition (i.e., polyurea particles and polyol carrier).
- PHD polyols have a viscosity in the range of from about 2,000 to about 6,000 centipoise.
- PIPA polyols are similar to PHD polyols but contain polyurethane particles instead of polyurea particles.
- the polyurethane particles in PIPA polyols are formed in situ by reaction of an isocyanate and alkanolamine (e.g., triethanolamine).
- the solids content of the PIPA polyols is typically up to about 80%, usually in the range of from about 15% to about 70%, by weight of the total weight of the composition (i.e., polyurethane particles and polyol carrier).
- PIPA polyols have a viscosity in the range of from about 4,000 to about 50,000 centipoise. See, for example, U.S. Pat. Nos. 4,374,209 and 5,292,778.
- Epoxy dispersion polyols are based on dispersions of cured epoxy resins in conventional based polyols. The epoxy particles are purportedly high modulus solids with improved hydrogen bonding characteristics.
- the present invention provides a foamed isocyanate-based polymer derived from a reaction mixture comprising an isocyanate, an active hydrogen-containing compound, a dendritic macromolecule and a blowing agent; wherein at least a 15% by weight of the dendritic macromolecule may be mixed with a polyether polyol having an OH number less than about 40 mg KOH/g to form a stable liquid at 23° C.
- the present invention provides a foamed isocyanate-based polymer derived from an isocyanate and an active hydrogen-containing compound, the polymer having a cellular matrix comprising a plurality of interconnected struts, the active hydrogen-containing compound conferring to the cellular matrix a load efficiency of at least about 15 Newtons (preferably from about 15 to about 50 Newtons, more preferably from about 20 to about 45 Newtons, most preferably from about 25 to about 35 Newtons).
- the present invention provides a foamed isocyanate-based polymer having a cellular matrix comprising a plurality of interconnected struts, the cellular matrix: (i) having a load efficiency of at least about 15 Newtons, and (ii) being substantially free of particulate material.
- the present invention provides a process for producing a foamed isocyanate-based polymer comprising the steps of:
- the dendritic macromolecule may be mixed with a polyether polyol having an OH number less than about 40 mg KOH/g to form a stable liquid at 23° C.
- the present invention provides a foamed isocyanate-based polymer derived from a reaction mixture comprising an isocyanate, an active hydrogen-containing compound, a dendritic macromolecule and a blowing agent; the foamed isocyanate-based polymer having an Indentation Force Deflection loss when measured pursuant to ASTM D3574 which is less than that of a reference foam produced by substituting a copolymer polyol for the dendritic macromolecule in the reaction mixture, the foamed isocyanate-based polymer and the reference foam having substantially the same density and Indentation Force Deflection when measured pursuant to ASTM D3574 (50 in 2 indentor; 15′′ ⁇ 15′′ ⁇ 4′′ sample size; 25° C., 50% relative humidity.
- the present invention provides a foamed isocyanate-based polymer derived from a reaction mixture comprising an isocyanate, an active hydrogen-containing compound, a dendritic macromolecule and a blowing agent; the foamed isocyanate-based polymer having thickness loss when measured pursuant to ASTM D3574 which is less than that of a reference foam produced by substituting a copolymer polyol for the dendritic macromolecule in the reaction mixture, the foamed isocyanate-based polymer and the reference foam having substantially the same density and Indentation Force Deflection when measured pursuant to ASTM D3574.
- isocyanate-based polymer is intended to mean, inter alia, polyurethane, polyurea and polyisocyanurate.
- dendritic polymer and “dendritic macromolecule” are used interchangeably throughout this specification. These materials are generally known in the art. See, for example, any one of:
- the present inventors have surprisingly and unexpectedly discovered that a sub-group of dendritic macromolecules is particularly advantageous to confer load building properties in an isocyanate-based foam. Indeed, as will be developed in the Examples hereinbelow, its possible to utilize the sub-group of dendritic macromolecules to partially or fully displace copolymer polyols conventionally used to confer load building characteristics to isocyanate-based polymer foams.
- the sub-group of dendritic macromolecules is described in detail in copending U.S. patent application Ser. No. 60/221,512, filed on Jul. 28, 2000 in the name of Pettersson et al. and the contents of which are hereby incorporated by reference.
- Preferred aspects of the present invention relate to the ability to mix at least about 15% by weight of the dendritic macromolecule with a polyether polyol having an OH number less than about 40 mg KOH/g to form a stable liquid at 23° C.
- stable liquid when used in connection with this solubility parameter of the dendritic macromolecule, is intended to mean that the liquid formed upon mixing the dendritic macromolecule and the polyol has a substantial constant light transmittance (transparent at one extreme and opaque at the other extreme) for at least 2 hours, preferably at least 30 days, more preferably a number of months, after production of the mixture.
- the stable liquid will be in the form a clear, homogeneous liquid (e.g., a solution) which will remain as such over time.
- the stable liquid will be in the form an emulsion of (at least a portion of) the dendritic macromolecule in the polyol which will remain as such over time - i.e., the dendritic macromolecule will not settle out over time.
- the present invention is related to foamed isocyanate-based polymer and to a process for production thereof.
- the isocyanate-based polymer is selected from the group comprising polyurethane, polyurea, polyisocyanurate, urea-modified polyurethane, urethane-modified polyurea, urethane-modified polyisocyanurate and urea-modified polyisocyanurate.
- the term “modified”, when used in conjunction with a polyurethane, polyurea or polyisocyanurate means that up to 50% of the polymer backbone forming linkages have been substituted.
- the present foamed isocyanate-based polymer is produced from a reaction mixture which comprises an isocyanate and an active hydrogen-containing compound.
- the isocyanate suitable for use in the reaction mixture is not particularly restricted and the choice thereof is within the purview of a person skilled in the art.
- the isocyanate compound suitable for use may be represented by the general formula:
- i is an integer of two or more and Q is an organic radical having the valence of i.
- Q may be a substituted or unsubstituted hydrocarbon group (e.g., an alkylene or arylene group).
- Q may be represented by the general formula:
- Q 1 is an alkylene or arylene group and Z is chosen from the group comprising —O—, —O—Q 1 —, —CO—, —S—, —S—Q 1 —S— and —SO 2 —.
- isocyanate compounds which fall within the scope of this definition include hexamethylene diisocyanate, 1 ,8-diisocyanato-p-methane, xylyl diisocyanate, (OCNCH 2 CH 2 CH 2 CH 2 O) 2 , 1-methyl-2,4-diisocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, chlorophenylene diisocyanates, diphenyhnethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4′,4′′-triisocyanate and isopropylbenzene-alpha-4-diisocyanate.
- Q may also represent a polyurethane radical having a valence of i.
- Q(NCO) i is a compound which is commonly referred to in the art as a prepolymer.
- a prepolymer may be prepared by reacting a stoichiometric excess of an isocyanate compound (as defined hereinabove) with an active hydrogen-containing compound (as defined hereinafter), preferably the polyhydroxyl-containing materials or polyols described below.
- the polyisocyanate may be, for example, used in proportions of from about 30 percent to about 200 percent stoichiometric excess with respect to the proportion of hydroxyl in the polyol. Since the process of the present invention may relate to the production of polyurea foams, it will be appreciated that in this embodiment, the prepolymer could be used to prepare a polyurethane modified polyurea.
- the isocyanate compound suitable for use in the process of the present invention may be selected from dimers and trimers of isocyanates and diisocyanates, and from polymeric diisocyanates having the general formula:
- i is an integer having a value of 1 or more and L is a monofunctional or polyfunctional atom or radical.
- isocyanate compounds which fall with the scope of this definition include ethylphosphonic diisocyanate, phenylphosphonic diisocyanate, compounds which contain a ⁇ Si—NCO group, isocyanate compounds derived from sulphonamides (QSO 2 NCO), cyanic acid and thiocyanic acid.
- Non-limiting examples of suitable isocyanates include: 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate, furfurylidene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylpropane diisocyanate, 4,4′-diphenyl-3,3′-dimethyl methane diisocyanate, 1,5-naphthalene diisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene, 2,4-diisocyanato-s-triazine, 1-methyl-2,4-diisocyanato cyclohexane, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,
- a more preferred isocyanate is selected from the group comprising 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, for example, a mixture comprising from about 75 to about 85 percent by weight 2,4-toluene diisocyanate and from about 15 to about 25 percent by weight 2,6-toluene diisocyanate.
- Another more preferred isocyanate is selected from the group comprising 2,4′-diphenylmethane diisocyanate, 4,4′-diphenyhnethane diisocyanate and mixtures thereof.
- the most preferred isocyanate is a mixture comprising from about 15 to about 25 percent by weight 2,4′-diphenylmethane diisocyanate and from about 75 to about 85 percent by weight 4,4′-diphenylmethane diisocyanate.
- the active hydrogen-containing compound is typically a polyol.
- the choice of polyol is not particularly restricted and is within the purview of a person skilled in the art.
- the polyol may be a hydroxyl-terminated backbone of a member selected from the group comprising polyether, polyester, polycarbonate, polydiene and polycaprolactone.
- the polyol is selected from the group comprising hydroxyl-terminated polyhydrocarbons, hydroxyl-terminated polyformals, fatty acid triglycerides, hydroxyl-terminated polyesters, hydroxymethyl-terminated polyesters, hydroxymethyl-terminated perfluoromethylenes, polyalkyleneether glycols, polyalkylenearyleneether glycols and polyalkyleneether triols. More preferred polyols are selected from the group comprising adipic acid-ethylene glycol polyester, poly(butylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene—see, for example, British patent number 1,482,213, for a discussion of suitable polyols.
- such a polyether polyol has a molecular weight in the range of from about 200 to about 10,000, more preferably from about 2,000 to about 7,000, most preferably from about 2,000 to about 6,000.
- the active hydrogen-containing compound comprises compounds wherein hydrogen is bonded to nitrogen.
- such compounds are selected from the group comprising polyamines, polyamides, polyimines and polyolamines, more preferably polyamines.
- Non-limiting examples of such compounds include primary and secondary amine terminated polyethers.
- polyethers Preferably such polyethers have a molecular weight of greater than about 230 and a functionality of from 2 to 6.
- Such amine terminated polyethers are typically made from an appropriate initiator to which a lower alkylene oxide is added with the resulting hydroxyl terminated polyol being subsequently aminated.
- alkylene oxides may be present either as random mixtures or as blocks of one or the other polyether.
- the hydroxyl groups of the polyol be essentially all secondary hydroxyl groups.
- the amination step replaces the majority but not all of the hydroxyl groups of the polyol.
- the reaction mixture used to produce the present foamed isocyanate-based polymer typically will further comprise a blowing agent.
- a blowing agent As is known in the art water can be used as an indirect or reactive blowing agent in the production of foamed isocyanate-based polymers. Specifically, water reacts with the isocyanate forming carbon dioxide which acts as the effective blowing agent in the final foamed polymer product. Alternatively, the carbon dioxide may be produced by other means such as unstable compounds which yield carbon dioxide (e.g., carbamates and the like).
- direct organic blowing agents may be used in conjunction with water although the use of such blowing agents is generally being curtailed for environmental considerations.
- the preferred blowing agent for use in the production of the present foamed isocyanate-based polymer comprises water.
- the amount of water used as an indirect blowing agent in the preparation of a foamed isocyanate-based polymer is conventionally in the range of from about 0.5 to as high as about 40 or more parts by weight, preferably from about 1.0 to about 10 parts by weight, based on 100 parts by weight of the total active hydrogen-containing compound content in the reaction mixture.
- the amount of water used in the production of a foamed isocyanate-based polymer typically is limited by the fixed properties expected in the foamed polymer and by the tolerance of the expanding foam towards self structure formation.
- the reaction mixture used to produce the present foamed isocyanate-based polymer typically will further comprise a catalyst.
- the catalyst used in the reaction mixture is a compound capable of catalyzing the polymerization reaction.
- Such catalysts are known, and the choice and concentration thereof in the reaction mixture is within the purview of a person skilled in the art. See, for example, U.S. Pat. Nos. 4,296,213 and 4,518,778 for a discussion of suitable catalyst compounds.
- suitable catalysts include tertiary amines and/or organometallic compounds.
- a Lewis acid must be used as the catalyst, either alone or in conjunction with other catalysts. Of course it will be understood by those skilled in the art that a combination of two or more catalysts may be suitably used.
- a dendritic macromolecule is incorporated in the present foamed isocyanate-based polymer.
- the dendritic macromolecule has the following characteristics:
- (iii) at least about 15%, more preferably from about 15% to about 50%, even more preferably from about 15% to about 40%, even more preferably from about 15% to about 30%, by weight of the dendritic macromolecule may be mixed with a polyether polyol having an OH number less than about 40, more preferably from about 25 to about 35, mg KOH/g to form a stable liquid at 23° C.
- additives in the polyurethane foam art can be incorporated in the reaction mixture created during the present process.
- additives include: surfactants (e.g., organo-silicone compounds available under the tradename L-540 Union Carbide), cell openers (e.g., silicone oils), extenders (e.g., halogenated paraffins commercially available as Cereclor S45), cross-linkers (e.g., low molecular weight reactive hydrogen-containing compositions), pigments/dyes, flame retardants (e.g., halogenated organo-phosphoric acid compounds), inhibitors (e.g., weak acids), nucleating agents (e.g., diazo compounds), anti-oxidants, and plasticizers/stabilizers (e.g., sulphonated aromatic compounds).
- surfactants e.g., organo-silicone compounds available under the tradename L-540 Union Carbide
- cell openers e.g., silicone oils
- extenders e.g., halogen
- the following Examples illustrate the use of the dendritic polymer in a typical isocyanate-based high resilience (HR) based foam.
- the isocyanate-based foam was prepared by the pre-blending of all resin ingredients including polyols, copolymer polyols, catalysts, water, and surfactants as well as the dendritic macromolecule of interest. The isocyanate was excluded from this mixture.
- the resin blend and isocyanate were then mixed at an isocyanate index of 100 using a conventional two-stream mixing technique and dispensed into a preheated mold (65° C.) having the dimensions 38.1 cm ⁇ 38.1 cm ⁇ 10.16 cm. The mold was then closed and the reaction allowed to proceed until the total volume of the mold was filled. After approximately 6 minutes, the isocyanate-based foam was removed and, after proper conditioning, the properties of interest were measured. This methodology will be referred to in the following Examples as the General Procedure.
- E837 base polyol, commercially available from Lyondell;
- E850 a 43% solids content copolymer(SAN)polyol, commercially available from Lyondell;
- HBP a dendritic macromolecule produced in Example A hereinbelow and discussed in more detail in copending U.S. patent application Ser. No. 60/221,512, filed on Jul. 28, 2000 in the name of Pettersson et al.;
- DEAO LF diethanolamine
- cross-linking agent commercially available from Air Products
- Glycerin a cross-linking agent, commercially available from Van Waters & Rogers;
- Dabco 33LV a gelation catalyst, commercially available from Air Products
- Niax A-1 a blowing catalyst, commercially available from Witco;
- DC 5169 a surfactant, commercially available from Air Products
- Y-10184 a surfactant, commercially available from Witco.
- the obtained dendritic polymer had the following characteristics: Final acid value: 8.9 mg KOH/g Final hydroxyl value: 489 mg KOH/g Peak molecular weight: 3490 g/mole Mw (SEC): 3520 g/mole Mn (SEC): 2316 g/mole PDI (Mw/Mn): 1.52 Average hydroxyl functionality: 30.4 OH-groups/molecule
- reaction was allowed to continue for a further 1.5 hours at 170° C., after which the reaction temperature was increased to 180° C.
- the reaction mixture was kept at this temperature for a further 2.5 hours until an acid value of 5.7 mg KOH/g was obtained. Full vacuum was then applied to the reactor to remove all xylene from the final product.
- the obtained derivatized dendritic polymer had the following characteristics: Final acid value: 6.2 mg KOH/g Final hydroxyl value: 293 mg KOH/g Peak molecular weight: 4351 g/mole Mw (SEC): 4347 g/mole Mn (SEC): 1880 g/mole PDI (Mw/Mn): 2.31 Average hydroxyl functionality: 22.7 OH-groups/molecule
- isocyanate-based foams based on the formulations shown in Table 1 were produced using the General Procedure referred to above.
- isocyanate-based foams were prepared having a copolymer polyol concentration of 7% (Examples 1 and 3) and 11% (Examples 2 and 4) by weight of resin and having a % H 2 O concentration of 3.80% which results in an approximate foam core density of 31 kg/m 3 .
- the dendritic macromolecule concentration was increased from 2% by weight of resin (Examples 1 and 2) to 5% by weight of resin (Examples 3 and 4).
- a “load efficiency”, having units of Newtons/weight % dendritic macromolecule in the resin blend, for each foam may be reported and represents the ability of the dendritic macromolecule to generate firmness in the isocyanate-based foam matrix.
- the term “load efficiency” is defined as the number of Newtons of foam hardness increase per weight % of the dendritic macromolecule added to a base or control resin blend (i.e., typically comprising all ingredients in the foamable composition except the iscocyanate).
- the term “load efficiency”, as used throughout this specification, is intended to have the meaning set out in this paragraph.
- the load efficiency of the dendritic macromolecule was determined to be 23.78 Newtons/weight % dendritic macromolecule in the resin blend while for Examples 2 and 4, the load efficiency was determined to be 33.42 Newtons/weight % dendritic macromolecule in the resin blend.
- isocyanate-based foams were prepared having copolymer polyol concentrations as those used in Examples 1-4 with a % H 2 O concentration of 3.2% which results in an approximate core foam density of 36kg/m 3 .
- the dendritic macromolecule concentration was increased from 2% to 5% by weight of resin.
- isocyanate based foams were prepared in the absence of any copolymer polyol.
- the isocyanate-based foams were formulated with a % H 2 O concentration of 3.8% resulting in an approximate foam core density of 31 kg/m 3 .
- the level of the dendritic macromolecule was varied from 6.68% to 13.35% by weight in the resin.
- isocyanate based foams were prepared in the absence of any copolymer polyol.
- the isocyanate-based foams were formulated with a %H 2 O concentration of 3.2% resulting in an approximate foam core density of 36 kg/m 3 .
- the level of the dendritic macromolecule was varied from 6.72% to 13.43% by weight in the resin.
- isocyanate based foams were prepared in the absence of any dendritic macromolecule and used only copolymer polyol as the method by which foam hardness is increased.
- Examples 15 and 16 are provided for comparative purposes only and are outside the scope of the present invention.
- the isocyanate-based foams were formulated with a %H 2 O concentration of 3.8% resulting in an approximate foam core density of 31 kg/m 3 .
- the level of the copolymer polyol was varied from 26% to 8% by weight in the resin.
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| US12/164,615 US7939574B2 (en) | 2000-07-28 | 2008-06-30 | Foamed isocyanate-based polymer having improved hardness properties and process for production thereof |
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| WO2011057018A1 (en) | 2009-11-04 | 2011-05-12 | Stepan Company | Method of improving mechanical strength of flexible polyurethane foams made from bio-based polyols, the polyol compositions utilized therein and the foams produced thereby |
| US20110257284A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Process for producing flame-retardant pu foams |
| MX2019000084A (es) * | 2016-06-29 | 2019-06-17 | Proprietect Lp | Polímero espumado a base de isocianato. |
| CN106632980B (zh) * | 2016-12-30 | 2019-08-16 | 山东一诺威聚氨酯股份有限公司 | 一种稳定ndi预聚体及其制备方法和应用 |
| CN110527479B (zh) * | 2019-08-19 | 2021-05-18 | 济南大学 | 一种超支化型热塑性聚氨酯胶黏剂及其在消防水带中的应用 |
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- 2001-07-30 AT AT01953735T patent/ATE460445T1/de not_active IP Right Cessation
- 2001-07-30 MX MXPA02012835A patent/MXPA02012835A/es active IP Right Grant
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- 2001-07-30 JP JP2002515974A patent/JP2004505140A/ja active Pending
- 2001-07-30 US US09/917,235 patent/US20020061936A1/en not_active Abandoned
- 2001-07-30 CZ CZ20021811A patent/CZ20021811A3/cs unknown
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| US5418301A (en) * | 1992-02-26 | 1995-05-23 | Perstorp Ab | Dendritic macromolecule and process for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8293808B2 (en) | 2003-09-30 | 2012-10-23 | Cargill, Incorporated | Flexible polyurethane foams prepared using modified vegetable oil-based polyols |
| US20050070620A1 (en) * | 2003-09-30 | 2005-03-31 | Ron Herrington | Flexible polyurethane foams prepared using modified vegetable oil-based polyols |
| US7786239B2 (en) | 2004-06-25 | 2010-08-31 | Pittsburg State University | Modified vegetable oil-based polyols |
| US20060041157A1 (en) * | 2004-06-25 | 2006-02-23 | Petrovic Zoran S | Modified vegetable oil-based polyols |
| US8153746B2 (en) | 2004-06-25 | 2012-04-10 | Cargill, Incorporated | Modified vegetable oil-based polyols |
| US20070249484A1 (en) * | 2004-07-21 | 2007-10-25 | Johannes Benkhoff | Process for the Photoactivation and use of a Catalyst by an Inverted Two-Stage Procedure |
| US7691914B2 (en) | 2005-04-25 | 2010-04-06 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
| US20100184878A1 (en) * | 2005-04-25 | 2010-07-22 | Cargill, Incorporated | Polyurethane foams comprising oligomeric polyols |
| WO2006128872A1 (de) * | 2005-06-03 | 2006-12-07 | Basf Aktiengesellschaft | Poröse polyisocyanat-polyadditionsprodukte |
| US20080188577A1 (en) * | 2005-06-03 | 2008-08-07 | Basf Aktiengeseelschaft | Porous Polyisocyanate Polyaddition Products |
| US8067480B2 (en) * | 2005-06-03 | 2011-11-29 | Basf Se | Porous polyisocyanate polyaddition products |
| CN101184788B (zh) * | 2005-06-03 | 2010-11-10 | 巴斯福股份公司 | 多孔聚异氰酸酯加聚产物 |
| US20070078193A1 (en) * | 2005-08-31 | 2007-04-05 | Gilder Stephen D | Strut-reinforced, reduced VOC polyurethane foam |
| US20070066697A1 (en) * | 2005-08-31 | 2007-03-22 | Gilder Stephen D | Strut-reinforced polyurethane foam |
| US20100174006A1 (en) * | 2005-09-20 | 2010-07-08 | Sleep Innovations, Inc. | Strut-Reinforced, Reduced VOC Polyurethane Foam |
| WO2008071622A1 (de) * | 2006-12-11 | 2008-06-19 | Basf Se | Hochelastische polyurethanweichschaumstoffe |
| US20090287007A1 (en) * | 2008-05-13 | 2009-11-19 | Cargill, Incorporated | Partially-hydrogenated, fully-epoxidized vegetable oil derivative |
| US20110275732A1 (en) * | 2009-01-12 | 2011-11-10 | Basf Se | Highly elastic flexible polyurethane foams |
| CN102341420A (zh) * | 2009-01-12 | 2012-02-01 | 巴斯夫欧洲公司 | 高弹性柔性聚氨酯泡沫体 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002010247A1 (en) | 2002-02-07 |
| CA2394563C (en) | 2010-01-26 |
| CA2394563A1 (en) | 2002-02-07 |
| JP2004505140A (ja) | 2004-02-19 |
| NO20022418D0 (no) | 2002-05-22 |
| AU7622601A (en) | 2002-02-13 |
| EP1248809A1 (en) | 2002-10-16 |
| US7939574B2 (en) | 2011-05-10 |
| DE60141502D1 (de) | 2010-04-22 |
| MXPA02012835A (es) | 2003-05-21 |
| AU777710B2 (en) | 2004-10-28 |
| PL356275A1 (en) | 2004-06-28 |
| US20080269369A1 (en) | 2008-10-30 |
| BR0107276B1 (pt) | 2010-11-16 |
| CZ20021811A3 (cs) | 2003-03-12 |
| ATE460445T1 (de) | 2010-03-15 |
| BR0107276A (pt) | 2002-08-27 |
| EP1248809B1 (en) | 2010-03-10 |
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| AS | Assignment |
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Owner name: PROPRIETECT L.P., CANADA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WOODBRIDGE FOAM CORPORATION;REEL/FRAME:022746/0204 Effective date: 20070301 |