AU679645B2 - Self-releasing binder system for composite products - Google Patents
Self-releasing binder system for composite products Download PDFInfo
- Publication number
- AU679645B2 AU679645B2 AU29155/95A AU2915595A AU679645B2 AU 679645 B2 AU679645 B2 AU 679645B2 AU 29155/95 A AU29155/95 A AU 29155/95A AU 2915595 A AU2915595 A AU 2915595A AU 679645 B2 AU679645 B2 AU 679645B2
- Authority
- AU
- Australia
- Prior art keywords
- polyether
- containing compound
- polyisocyanate
- line
- document
- 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.)
- Expired - Fee Related
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- 239000011230 binding agent Substances 0.000 title claims description 39
- 239000002131 composite material Substances 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 115
- 229920000570 polyether Polymers 0.000 claims description 96
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 95
- 239000005056 polyisocyanate Substances 0.000 claims description 77
- 229920001228 polyisocyanate Polymers 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 64
- -1 carbamayl Chemical group 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 29
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 229910019142 PO4 Inorganic materials 0.000 claims description 24
- 235000021317 phosphate Nutrition 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 15
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 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 9
- 150000007513 acids Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 229910052717 sulfur Chemical group 0.000 claims description 7
- 239000011593 sulfur Chemical group 0.000 claims description 7
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical class O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- DKJBREHOVWISMR-UHFFFAOYSA-N 1-chloro-2,3-diisocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1N=C=O DKJBREHOVWISMR-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 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 2
- KDLIYVDINLSKGR-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenoxy)benzene Chemical compound C1=CC(N=C=O)=CC=C1OC1=CC=C(N=C=O)C=C1 KDLIYVDINLSKGR-UHFFFAOYSA-N 0.000 claims 1
- 229920002614 Polyether block amide Polymers 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000007944 thiolates Chemical class 0.000 claims 1
- 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 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 18
- 239000002023 wood Substances 0.000 description 14
- 229910000975 Carbon steel Inorganic materials 0.000 description 13
- 239000010962 carbon steel Substances 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241000183024 Populus tremula Species 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229920002396 Polyurea Polymers 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 235000011180 diphosphates Nutrition 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid ester group Chemical group C(CCCCCCCCCCC)(=O)O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 210000000569 greater omentum Anatomy 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920003226 polyurethane urea Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
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- 150000002889 oleic acids Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical class [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
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- 101100409194 Rattus norvegicus Ppargc1b gene Proteins 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 235000005822 corn Nutrition 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- ZHGASCUQXLPSDT-UHFFFAOYSA-N cyclohexanesulfonic acid Chemical compound OS(=O)(=O)C1CCCCC1 ZHGASCUQXLPSDT-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- JCMJASXPAJYPLL-UHFFFAOYSA-N didecyl phosphono phosphate Chemical class CCCCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCCCC JCMJASXPAJYPLL-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004000 hexols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 1
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000162 poly(ureaurethane) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000010904 stalk Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- IWPOSDLLFZKGOW-AATRIKPKSA-N trans-beta-octenoic acid Chemical compound CCCC\C=C\CC(O)=O IWPOSDLLFZKGOW-AATRIKPKSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 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
- C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
-
- 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
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- 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
- C08G2125/00—Compositions for processes using internal mould release agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
WO 96/01293 PCTIUS95/08333 SELF-RELEASING BINDER SYSTEM FOR COMPOSITE PRODUCTS This invention relates -o binders useful in preparing composite products. More particularly, it relates to composite products prepared from comminuted, preferably lignocellulosic, materials.
The use of organic polyisocyanates as adhesive binders in preparing board products from comminuted woodstock, including wood flakes, chips, strands or fibers, is well-known. References to such use include, for example, U.S. Patents Nos. 3,428,592, 3,440,180; 3,557,263; 3,636,199; 3,870,665; 3,919,017; and 3,930,110. In a typical process the binder resins, optionally in the form of a solution or aqueous suspension or emulsion, are applied to or admixed with the particles of cellulosic material, or other types of substrate material capable of forming composite articles, using a tumbler apparatus, blender or other form of agitator. The mixture of particles and binder is then formed into a mat and subjected to heat and pressure using heated platens. The process can be carried out in a batch operati3n or continuously.
To avoid adhesion of the composite board or other article to the heated platens, it has hitherto been necessary to interpose a sheet impermeable to isocyanate, between the surface of the board and the platen during the forming process, or to coat the surface of the platen, prior to each molding operation, with an appropriate release agent. Another approach has been to coat the surface of the particles themselves with a material which will not adhere to the platen. Any of these choices, pa ticularly where the process is being operated on a continuous basis, is cumbersome and a drawback to what is otherwise a very satisfactory method of making the composite article with highly attractive structural strength properties.
To obtain release it has also been suggested that an acid phosphate be added to the isocyanate compound as an "internal I I WO 96/01293 PCT/US95/08333 release agent", as described in U.S. Patent 4,257,995. This system appears to provide release from aluminum platens, but has shown extremely poor release from steel. Other mold release systems suffering similar disadvantages include use of a polymerized fatty acid and/or a polycarboxyl compound containing a polymeric fatty radical in conjunction with an isocyanate, as disclosed in U.S.
Patent 4,933,232, or a sulfonic acid in conjunction with an isocyanate, as disc'-sed in U.S. Patent 4,528,153. Thus, it would be desirable to de p a binder system that provides good adhesion of the particles to be adhered, while also exhibiting good release from a wide variety of metal platens.
Summary of the Invention Accordingly, the present invention is a self-releasing binder composition prepared by contacting at least a polyisocyanate compound, a compound of one of the following formulae in an amount from about 1 to about 20 parts per 100 parts by weight of the polyisocyanate compound: x o o I II II RO p OH R C OH R S -OH I II OR' 0 (II) (11I) wherein X is oxygen or sulfur, R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic, and R' is R, H, or an acyl, carbamoyl, phosphoryl or sulfoiiyl group; and a polyether containing compound, with the following provisos: (i) wherein the polyether containing compound contains no active hydrogen, the polyether containing compound is present in an amount -2- -y I WO 96/01293 PCT/US95/08333 from about 1 to about 2000 parts per 100 parts by weight of the polyisocyanate; and (ii) wherein the polyether containing compound contains at least one active hydrogen, the polyether containing compound is present in an amount such that, for compounds of Formula I, the OH:NCO equivalency ratio is less than about 0.77:1.00; for compounds of Formula II, the OH:NCO equivalency ratio is less than about 0.25:1.00; and for compounds of Formula III, the OH:NCO equivalency ratio is less than about 0.10:1.00; under reaction conditions sufficient to form a binder composition.
In another embodiment the present invention is a process for preparing a composite article comprising contacting at least (1) a polyisocyanate compound; a compound of one of the following formulae in an amount from about 1 to about 20 parts per 100 parts by weight of the polyisocyanate: X 0 o 1 II 11 RO PI II R c H R S 0
OR'
(II(I) (II n wherein X is oxygen or sulfur, R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic, and R' is R, H, or an acyl, carbamoyl, phosphoryl or sulfonyl group; a polyether containing compound, with the following provisos: (i) wherein the polyether containing compound lacks an active hydrogen, the polyether containing compound is present in an amount from about 1 to about 2000 parts per 100 parts by weight of the polyisocyanate; and (ii) wherein the polyether containing compound contains at least one active hydrogen, the polyether containing compound is present in an amount such that, for compounds of Formula I, the OH:NCO equivalency ratio is less than about 0.77:1.00; for compounds of Formula II, the OH:NCO equivalency ratio is less than about I ii I s WO 96/01293 PCT/US95/08333 0.25:1.00; and for compounds of Formula III, the OH:NCO equivalency ratio is less than about 0.10:1.00; and substrate particles; under reaction conditions sufficient to form a composite article.
The self-releasing binder composition, comprising components and as described hereinabove, allows for excellent binding and maintenance of the internal bond strength of the substrate particles to be compacted to form the composite article. These substrate particles may include inorganic, polymeric, or other organic or, particularly, cellulosic particles such as wood flakes, chips, particles, strands or fibers, or other comminuted substrates. Additionally, the binder system provides for easy release of the final composite article from aluminum, steel, or other types of metal molds or platens. It thus is ideally suited for uses such as continuous commercial board production lines, where rapid, easy release is sought.
In the practice of the present invention the first required component of the self-releasing binder system, defined as comprising at least components and as described herein, is a polyisocyanate' As used herein, "polyisocyanate" refers to any isocyanate having an average functionality of 2 or greater, an average of at least two isocyanate groups per molecule. Thus, diisocyanates are encompassed thereby. Illustrative of organic polyisocyanates are diphenyl-methane diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, a,a -xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and the mixtures of these two isomers which are available commercially, triphenylmethane triisocyanates, 4,4'-diisocyanate-diphenyl ether, and polymethylene polyphenyl polyisocyanates. The latter polyisocyanates are mixtures containing from about 25 to about percent by weight of methylenebis(phenyl isocyanate), the remainder of the mixture being polymethylene polyphenyl polyisocyanates of functionality equal to or greater than about 2.0. Such polyisocyanates and methods for their preparation are well-known in the art; see, for example, U.S. Pat. Nos. 2,683,730; 2,950,263; L I LI WO 96/01293 PCT/US95/08333 3,012,008 and 3,097,191. These polyisocyanates are also available in various modified forms. One such form comprises a polymethylene polyphenyl polyisocyanate.
The polymethylene polyphenyl polyisocyanates are the preferred polyisocyanates for use in the binder systems of the invention. Particularly pref"rred polymethylene polyphenyl polyisocyanates are those which contain from about 35 to about percent by weight of methylene bis(phenylisocyanate).
The organic polyisocyanate can, in one embodiment of the present invention, be employed in the binder system in the form of an aqueous emulsion or dispersion. In this case the aqueous emulsion or dispersion can be prepared using any of the techniques known in the art for the preparation of such, prior to use of the composition in the binder. Illustratively, the polyisocyanate can be dispersed in water in the presence of an emulsifying agent. The latter can be any of the emulsifying agents known in the art, including anionic and nonionic agents. Illustrative of nonionic emulsifying agents are polyoxyethylene and polyoxy-propylene alcohols and block copolymers of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene; alkoxylated alkylphenols such as nonylphenoxy poly(ethyleneoxy)ethanols; alkoxylated aliphatic alcohols such as ethoxylated and propoxylated aliphatic alcohols containing from about 4 to 18 carbon atoms; glycerides of saturated and unsaturated fatty acids such as stearic, oleic, and ricinoleic aci polyoxyalkylene esters of fatty acids such as stearic, lauric, and oleic acids; and fatty acid amides such as the dialkanolamides of fatty acids including, for example, stearic, lauric, and oleic acids. A detailed account of such materials is found in Encyclopedia of Chemical Technology, Second Edition, Vol. 19, pp. 531-554, Interscience Publishers, New York.
The formation of the emulsion or dispersion can be carried out at any time prior to its use with the binder covuposition. Any of the methods conventional in the art for the preparation of I I I WO 96/01293 PCT/US95/08333 aqueous emulsions can be employed in preparing the aqueous polyisocyanate emulsions, such as the use of an in-line mixer just prior to application of the polyisocyanate to the selected substrate particles.
In addition to the polyisocyanate the present invention utilizes an organic acid compound selected from compounds of the formulae: x 0 o I II 11 RO p OH R C -OH R S "OH I II OR' 0 (II) (III) wherein X is oxygen or sulfur, R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic, and R' is R, H, or an acyl, carbamoyl, phosphoryl or sulfonyl group. For simplicity of reference these materials are herein termed "organic acid-containing compounds", but included herein are all compounds adhering to the formulae hereinabove, whether or not such would be termed to be or contain "organic acids" in conventional nomenclature.
In the formulae shown above, R and R' are selected from the group consisting of alkyl having at least 3 carbon atoms, alkenyl having at least 3 carbon atoms, aryl, aryl substituted by at least one alkyl, alkyl substituted by from 1 to 2 acyloxy groups wherein the acyl group is the residue of an aliphatic monocarboxylic acid having at least 2 carbon atoms. Each of the groups R and R' in the various formulae set forth above can optionally be substituted by one or more inert substituents, substituents which do not contain active hydrogen atoms and which are therefore unreactive in the presence of the polyisocyanate. Illustrative of such inert Lh II-I WO 96/01293 PCT/US95/08333 substituents are alkoxy, alkylmercapto, alkenyloxy, alkenylmercapto, chloro, bromo, iodo, fluoro, cyano and the like.
The compounds therefore comprehended by the above formulae include, for example, acid phosphates, sulfonic acids and carboxylic acids. Also included are the organic acid anhydrides or mixed anhydrides, for example, o-monoacyl, carbamoyl, phosphoryl and sulfonyl derivatives of either group; polyphosphates including branched polyphosphates and cyclometaphosphates; and mixtures thereof.
The term "anhydrides" includes, in part, pyrophosphates and pyrosulfates derived from the phosphorus-containing compound or the sulfur-containing compound (III). The pyrophosphates and pyrosulfates are obtained from their respective acid phosphates or acid sulfates by reaction of the latter with a dehydrating agent, such as carbonyl chloride, aryl or alkyl monoisocyanates and polyisocyanates, N,N'-dihydrocarbylcarbodiimides, and the like, in accordance with procedures well-known in the art; see, for example, F. Cramer and M. Winter, Chem. Ber. 94, 989 (1961); F. Ramirez, J.F.
Marecek and I. Ugi, J. Am. Chem. Soc. 97, 3809 (1975).
Preferred for the phosphorus- or sulfur-containing compound selection are liquid esters, including monoesters, diesters and combinations thereof, which are well-known, commercially available materials. If desired, the acid phosphates of Formula can be readily prepared in the form of mixtures of mono-and-diesters by reaction of an alcohol ROH or thiol RSH, wherein R is as defined above, with phosphorus pentoxide or oxysulfide in accordance with well-established procedures; see, for example, Kosolapoff, Organophosphorus Compounds, pp. 220-221, John Wiley and Sons, Inc., New York, 1950. Also preferred are the pyrophosphates or mixed pyrophosphates derived from mixtures of acid phosphates, and the pyrosulfates or mixed pyrosulfates derived from mixtures of sulfonic acids, readily obtained through methods cited above.
a a WO 96/01293 PCT/US95/08333 Illustrative of the phosphorus-containing compounds of Formula above which can be employed individually or in combination with other acid phosphates in the process of the invention are monoester acid phosphates such as mono-0-octyl, mono-O-nonyl and mono-O-decyl acid phosphate; diester phosphates such as O,O-di(octyl), O,O-di(nonyl) and O,0-di(decyl) acid phosphate; pyrophosphates such as tetraoctyl, tetranonyl and tetradecyl as well as di(octyl), di(nonyl) and di(decyl) pyrophosphates; and polyphosphates terminated with mono-0-octyl, mono-0-nonyl and mono-O-decyl groups, or 0,0-di(octyl), O,0-di(nonyl) and 0,0-di(decyl) groups, or mixed mono-0-octyl, O,0di(octyl) groups, or combinations of mono-0-alkyl and O,0-dialkyl groups of different chain lengths. It is apparent that acid phosphates and thiophosphates in which the esterifying radical is that derived from a monohydric alcohol which has been capped using the appropriate molar proportions of ethylene oxide, propylene oxide, epichlorohydrin or 1,1,1-trichlorobutylene oxide, are particularly advantageous in the present invention.
Additional phosphate compounds which are useful in this invention include monoacyl acid phosphates such as O-decanoyl, 0-dodecanoyl and 0-benzoyl derivatives, prepared as described by Kosolapoff, ibid, p. 334, and carbamoyl phosphates such as octenylcarbamoyl, decenylcarbamoyl and dodecenylcarbamoyl phosphates, prepared as described by F. Cramer and M. Winter, Chem.
Ber., pp. 92, 2761 (1959).
As shown by Formula (II) hereinabove, carboxylic and polycarboxylic acids are also useful in the present invention.
These can include, for example, straight and branched chain, polyand mono-ethylenically unsaturated acids such as 3-octenoic acid, 11-dodecanoic acid and 1,12-dodecanoic di(acid). The higher molecular weight polycarboxylic acids and polyfunctional carboxylic acids can be formulated to have a low viscosity for convenient spray I IL WO 96/01293 PCT/US95/08333 application, along with the other components of the present invention, to the substrate particles.
Particularly suitable sulfonic acids shown by Formula (III) hereinabove, include, for example, decane sulfunic acid, octadecane sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, cyclohexane sulfonic acid, and aromatic monosulfonic acids of the type which may be obtained in known manner by the sulfonation of alkyl benzenes such as hexyl-benzene, dodecyl-benzene, octadecyl-benzene or mixtures thereof.
In the practice of the present invention a polyether containing compound is also employed. The polyether containing compound can contain an active hydrogen, or can have, as its terminal or pendant groups, moieties that are not active hydrogens and are otherwise unreactive, that is, substantially inert, toward the polyisocyanate. As used herein, the "polyether containing compound" therefore includes any compound containing one or more polyether moieties, whether or not such would be classified by standard nomenclature as primarily or essentially a polyether compound.
In one embodiment, the polyether compound contains active hydrogens. Determination of whether there is an active hydrogen can be determined by use of the Zerewitinoff Test, as descr.Aed in J.B.
Niederl and V. Niederl, Micromethods of Quanitative Organic Analysis, p. 263 (New York 1946). In general the active hydrogen in such compounds reacts with polyisocyanates to form polyurethanes and related polymers, including polyureas and polyurethane/polyureas, and therefore, in some embodiments of the present invention the result is a polyurethane, polyurea or polyurethane/polyurea polymer binder. The active hydrogen containing compound is preferably a hydroxy-functional compound such as a polyol or monol. In general any polyether polyol typically employed in the art for preparation of polyurethane and related polymers, including so-called polyester b~ -1 WO 96/01293 PCT/US95/08333 polyols which contain polyether moieties (also called polyether polyester polyols), are suitable, and can have hydroxyl numbers which vary over a relatively wide range, preferably from 10, more preferably 100, to 6,000, more preferably to 600.
Preferred alcohols include polyols and monols selected from the following classes of compositions, alone or in admixture: (a) alkylene oxide adducts of poly-or-monohydroxy-alkanes or alkenes; alkylene oxide adducts of non-reducing sugars and sugar derivatives; alkylene oxide adducts of phosphorus and polyphosphorus acids; and alkylene oxide adducts of polyphenols.
Polyols of these types are referred to herein as "base polyols".
Examples of alkylene oxide adducts of polyhydroxyalkanes useful herein are adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxybutane, and 1,6-dihydroxyhexane, glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane, 1,1,l-trimethylolethane, 1,1,1-trimethylol-propane, pentaerythritol, polycaprolactone, xylitol, arabitol, sorbitol, mannitol, sucrose, various amines, mixtures thereof, and the like.
Also useful are poly(oxypropylene) glycols, triols. tetrols and hexols and any of these that are capped with ethylene oxide.
These polyols also include poly(oxypropyleneoxyethylene)polyols.
The ethylene oxide, when used, can be incorporated in any way along the polymer chain, for example, as internal blocks, terminal blocks, or randomly distributed blocks, or any combination thereof.
Additionally, polyester polyols and thiol compounds which contain polyether moieties are useful in this invention.
Other polyether containing compounds such as polyamines, amine-terminated polyols, polymercaptans and other isocyanate-reactive compounds are also suitable in the present invention. Another preferred class of polyols includes the "copolymer polyols", which are base polyols containing stably dispersed polymers such as acrylonitrile-styrene copolymers.
e I II WO 96/01293 PCT/US95/08333 Other types of polyether polyols useful in the process of the invention include polyurea polyols, such as are disclosed in U.S. Patents 3,325,421; 4,042, 537; 4,089,835; polyoxamate polyols, such as are disclosed in U.S. Patent 4,407,983; and polyisocyanatepolyaddition products, such as are disclosed in U.S. Patents 4,374,209; 4,324,716; 4,310,448; 4,310,449; 4,350,857; and 4,305,858.
Polyether containing compounds which do not possess active hydrogens are also useful for the practice of this invention. Inert reaction products of the polyether polyols, polyamines or polythiols heretofore described constitute an important group of these compounds. The term "inert" means that the reaction product is substantially unreactive with the polyisocyanate, in accordance with J.B. Niederl and V. Niederl, Micromethods of Quanitative Organic Analysis, p. 263 (New York 1946), in the self-releasing binder composition. These inert reaction products may be formed by addition of a polyether compound containing active hydrogens, epoxides or any group reactive with an isocyanate, to a stoichiometric excess of polyisocyanate, forming what are commonly termed as prepolymers, which contain at least one reactive isocyanate functional group. The prepolymer thus formed may contain polyurethane, polyurea, polythioure, or other moieties implicit in the prior description of the active hydrogen containing compounds.
A second group of inert reaction products of polyether polyols are those formed by esterification of the polyether polyol with organic acids or organic acid anhydrides. Polyethers comprising ethylene oxide, propylene oxide, butylene oxide and tetramethylene oxide, copolymers or mixtures thereof, and possessing mono-or-polyhydrox-' functionalities may thus be reacted with common acids or acid anhydrides through known procedures to prepare inert polyether esters. Examples of common acids are acetic, propionic, -11- L i C7l F I~--i4 I WO 96/01293 PCT/US95/08333 lauric, and toluene sulfonic acid, while acetic and phthalic anhydride are illustrative of common anhydrides.
A third group of inert polyether containing compounds can be prepared by reaction of a polyether polyol with monoisocyanates to form carbamoyl derivatives. Urea, thiourea, epoxide and siloxare derivatives are likewise available through reaction with corresponding polyether containing amine, thiol, epoxy and siloxane compounds, respectively. An example of a monoisocyanate that can be suitably employed is phenyl isocyanate.
Other polyether -ontaining compounds which are otherwise unreactive toward isocyanates, that is, which do not contain any active hydrogen, are tresylate, acrylate, aldehyde and succinimidyl derivatives of polyethylene glycol. Further examples of unreactive compounds are polyalkoxy ethers, polyalkoxy epoxides, polyalkoxy siloxanes, polyalkoxy amides, and polyalkoxy ketones wherein the pendant or terminal active hydrogens or functional groups have been reacted as hitherto described. Although this list is not considered comprehensive, it should be evident to those skilled in the art that various functional groups which can be rendered inactive toward polyisocyanates through standard chemistries will function within the scope of this invention, provided sufficient polyether content exists to effect release when used in conjunction with organic acids It is preferred that the weight ratio between such "inert" polyether containing compound and polyisocyanate be from 1, more preferably from 4, and most preferably from 6, to 2,000, more preferably 20, and most preferably 15, parts per 100 parts of polyisocyanate.
Mixtures of active hydrogen polyether containing compounds and inert polyether containing compounds can also be employed in. the present invention.
-12- L I WO 96/01293 PCT/US95/08333 Previously described are the constituents of the selfreleasing binder system itself. The starting materials for a composite article also comprise substrate particles. These particles are, in one preferred embodiment, cellulosic and capable of being compacted and bonded into the form of boards. Typical such materials are wood particles derived from lumber manufacturing waste such as planar shavings, veneer chips, and the like. Particles of other cellulosic material such as shredded paper, pulp or vegetable fibers such as corn stalks, straw, and bagasse, and of non-cellulosic materials such as scrap metals; polyurethane, polyisocyanurate, polyethylene and similar polymers; glass fibers; and combinations thereof, can also be used. Inorganic materials such as hydrated alumina, gypsum, and chopped mineral fibers can be employed, either alone or in combination with any of the above cellulosic or non-cellulosic materials, in the formation of particleboards or other composite articles in accordance with the present invention. If desired, mixtures of various types of cellulosic particles may also be used. If cellulosic particles are selected as the substrate material, it is generally preferred that the starting moisture content thereof is less than about 25 percent by weight.
In the present invention a number of different ways of contacting the starting materials, comprising the polyisocyanate organic acid compound polyether containing compound and substrate particles can be employed. In the first application method, segregated components and may be brought together simultaneously to be applied to the substrate particles. The term "simultaneously" implies the act of bringing together the segregated components prior to application to the substrate particles, whether it is accomplished through prior combination of and followed by contact with or, the act of bringing toqther is accomplished in a single stream which is fed by the hitherto se zegated components and -13- WO 96/01293 PCT/US95/08333 In one embodiment the selected organic acid containing compound is pre-blended with an active hydgrogen-containing polyether compound, such as a polyether polyol. Such generally forms a storage-stable composition which can be easily handled. In this case the weight ratio of the organic acid-containing compound to the active hydrogen containing polyether compound is preferably from 1:7600 to 1:0.10, more preferably from 1:275 to 1:0.70, and most preferably from 1:12 to 1:1. Simple blending, using any of a wide variety of methods and equipment well known to those skilled in the art, to ensure homogeneity, at ambient conditions of temperature and pressure, is preferred for reasons of convenience; however, a wide range of conditions from the freezing temperature of a given constituent to its boiling temperature can be used, since it is preferable that each component be a liquid. Thus, preferred temperatures range from 0°C, more preferably 15 0 C, to 70 0 C, more preferably 500C, and preferred pressures range from about 0 to about 3 atmospheres (atm). (1 atm equals 101,325 Pascals, or about 0.1 MPa.) Increased temperature or pressure can, in one embodiment, be employed to improve flow within the system where relatively viscous materials have been selected. It is preferable that the viscosity of the organic acid-containing compound/active hydrogen polyether containing compound blend be from 10, more preferably 50, to 5,000, more preferably 400, centipoise (cps). For some selections of component which are solid or not soluble in the polyether containing compound at room temperature, it is desirable to heat to their melting or solubility point in order to produce a homogeneous blend. In general it is preferred to use the higher monoester forms of liquid acid phosphates, such as 2-ethylhexyl- or isodecyl-, due to their greater ease of handling and compatibility with the polyol.
Following preparation of the blend including the polyether containing compound and organic acid the blend is then ready to be contacted with the polyisocyanate and applied to the cellulosic or other type of substrate particles. It is preferred that the weight ratio of the organic acid containing compound to the -14- WO 96/01293 PCT/US95/08333 polyisocyanate be from about 4, preferably from about 6, to about 12 parts, more preferably about 8 parts, organic acid-containing compound, to about 100 parts polyisocyanate. Because the polyisocyanate and active hydrogen polyether containing compound react to form a polyurethane and/or polyurea polymer, it is necessary, when the components are all mixed together prior to application to the particles, that such application occur within a relatively short period of time after mixing. In order to mix the polyisocyanate and isocyanate-reactive compound, any means, method, equipment or conditions generally known to or used by those skilled in the art of polyurethane and related polymer production may be used. These include, for example, impingement mixing to a spray head; simple mixing, as by hand or mechanical means on either a small or large scale; or by use of rollers or shakers. Since the reaction between the polyisocyanate and the isocyanate-reactive constituent of the blend is exothermic in nature, it is preferred that such contact be carried out at a temperature from 0°C, more preferably 20 0 C, to 50°C, more preferably 30 0
C.
In another embodiment of the present invention each of the components of the binder composition can be simultaneously mixed, as, for example, using a three-stream mixhead, without pre-blending of the organic acid compound with the polyether containing compound In still another embodiment the organic acid compound can be pre-blended with the polyisocyanate In this case it is prefercable that such pre-blending be accomplished just prior to contact with the polyether containing compound, since the polyisocyanate and organic acid compound may in some cases be reactive and therefore may not be sufficiently storage-stable.
In yet another embodiment, the components of the binder composition, and are combined and processed into a storage-stable material which is stored in a single container, until needed for application to the substrate particles It should be evident to those skilled in the art, that means are available for I I WO 96/01293 PCT/US95/08333 processing organic acid containing compounds through reaction with polyisocyanates such that reaction products are inert and no longer reactive toward polyisocyanates. Examples of this are found in US 4,258,169, US 4,478,738 and US 4,772,442. The polyether containing compound may be combined With the polyisocyanate (1) in a manner consistent with the presence or absence of active hydrogens in the compound. In one embodiment, a prepolymer of an active hydrogen polyether containing compound, such as a polyether polyol, can be formed by means well-established in the art. In a second embodiment, an inert polyether containing compound such as an esterified polyether monol, can be blended with a polyisocyanate.
For the polyether containing compound, whether or not it contains active hydrogens, the reaction or blending with the polyisocyanate can occur with a polyisocyanate which has already been reacted with the organic acid containing compound or, may first be reacted with or blended with the polyisocyanate which subsequently undergoes reaction with the organic acid containing compound, or, in cases wherein there is insignificant reactivity between the polyether containing compound and organic acid containing compound they may be added in concert to the polyisocyanate In general, it is preferred that and are processed into a liquid storage-stable mixture by heating the polyisocyanate at a temperature from about 60 0 C to about 190 0
C;
combining therewith, either simultaneously or subsequently, from about 1 to about 20 parts, per 100 parts of polyisocyanate, each of and to form a reaction mixture; maintaining the heating for a time such that no phase separation occurs upon cooling the reaction mixture to ambient temperatures. In a preferred embodiment, an organic acid is combined with a polyisocyanate over a temperature range from about 60 to about 190 0 C for two hours; then a polyether containing compound which contains no active hydrogens is added. Preferably, the organic acid is an acid phosphate; the polyisocyanate is a polymeric isocyanate, and the polyether containing compound is an esterified polyether monol. The organic -16- WO 96/01293 PCT/US95/08333 acid and the polyether containing compound are preferably used in an amount of 1 to 20 parts, based on 100 parts of polyisocyanate. In a still more preferred embodiment, 4-12 parts of acid phosphate and 6-20 parts of polyether containing compound, based on 100 parts of polyisocyanate, are used. It is also more preferred to use a temperature from 60-100 0 C. In this case the esterified polyether monol can be added at an elevated temperature to react oa.t minor amounts of active hydrogen containing impurities that may be present, in which case it is preferable to perform the addition at 60-80 0 C, maintaining this temperature for 0.5-1.5 hours until the impurities are rendered inert. In any case, heating is maintained for a time such that substantially no phase separation occurs upon cooling the reaction mixture to ambient. If no active hydrogen containing impurities are present, the esterified polyether monol can be blended with the polyisocyanate containing the reaction product of the acid phosphate, at ambient temperature. This selfreleasing binder composition is a liquid, storage-stable material and may be stored for a considerable period of time until desired for application to substrate particles.
In another preferred embodiment, a polyether polyol and an acid phosphate can be added to a stoichiometric excess of polyisocyanate maintained between 60-100 0 C for 2 to 3 hours.
The same proportions of materials as previously described are employed. The preferred polyisocyanate has a relatively high monomeric methylene bis(phenyl) isocyanate content, such that the viscosity of the final reaction product is preferably from 50 to 1000 cps, more preferably to 500 cps. If desired, a relatively low viscosity product can be blended with a higher order polymeric isocyanate to increase viscosity. Alternatively, a relatively high viscosity product, formed from a higher order polymeric isocyanate, can be blended with a polyisocyanate containing a significant proportion of methylene bis(phenyl) isocyanate to achieve a lower viscosity product. In either case, the amounts of reactants are -17- ~I r--lpli WO 96/01293 PCT/US95/08333 adjusted accordingly such that the final product falls within the preferred weight ranges.
Illustratively, a total of from about 2 to 8 percent by weight of the binder system (total constituent weight, excluding any moisture which may be present in the particles) is added, based on the "oven dry" weight of the particles, but higher or lower amounts of binder system may be used in any given application.
Illustratively, where the particles are of large size, such as in strand board and wafer board, it is possible to use amounts of binder less than 1 percent by weight, based on the "oven dry" weight of the particles. Where the particles are very small, that is, have a high surface area to volume ratio as in the case of powdered inorganic materials, it is desirable to use amounts of binder up to about 30 percent by weight, preferably to about 20 percent by weight. If desired, other materials, such as wax sizing agents, fire retardants, pigments, and combinations thereof, may also be added to the particles before or during thr a.C' tcation of the binder system to the substrate particles.
In a preferred embodiment of the present invention, the coated substrate particles are concurrently or subsequently formed into a loose mat or felt, preferably containing from 4 percent to percent moisture by weight. The mat is then placed in a heated press and compressed to consolidate the substrate particles into a compact composite article. Pressing times, temperatures and pressures vary widely depending on the thickness of the board produced, the desired density of the board, the size of the particles used, and other factors well known in the art. For example, for 0.5 inch thick particle board of medium density, pressures of from about 300 to about 700 psi and temperatures of from about 325'F to about 400*F are typical. Pressing times are typically from about 2 to about 5 minutes.
-18- I '~JI WO 96/01293 PCTUS95/08333 The above-described process can be carried out on a batch basis, that is, individual sheets of particle board can be molded by treating an appropriate amount of particles with the binder resin combination and heating and pressing the treated material.
Alternatively, the process can be carried out in a continuous manner by feeding treated particles in the form of a continuous web or mat through a heating and pressing zone defined by upper and lower continuous belts to which, and through which, the necessary heat and pressure are applied.
Whether the process of the invention is carried out in a batchwise or continuous manner, it has been found that composite articles produced using the self-releasing binder composition described herein release readily from the metal plates of the press used in their formation and show a significantly reduced tendency to stick or adhere to the platens, even when the platens are made of steel, as well as when the platens are made of other commonly used materials such as aluminum, chromium and nickel. This is in direct contrast to previous experience with the use of polyisocyanates alone, or polyisocyanates with acid phosphates, sulfates or carboxylates alone, on certain typez of platens, and particularly on steel.
The following preparations and examples are intended to illustrate the present invention and are not intended to be, nor should they be construed as being, limiting of its scope in any way.
As used in the examples, the following terms are defined as follows:
DOWANOL
TM 500 denotes a product available from The Dow Chemical Company which is a 500 molecular weight monol prepared from heterofed ethylene oxide and propylene oxide.
-19- ~3331 i r i WO 96/01293 PCT/US95/08333 P-425, denotes a product available from The Dow Chemical Company which is a 425 molecular weight propylene oxide-based polyether polyol.
E-400, denotes a product available from The Dow Chemical Company which is a 400 molecular weight ethylene oxide-based polyether diol.
ETHFAC
TM PD-0, denotes a product available from Ethox Corporation which is a high mono-ester isodecyl acid phosphate.
ETHOX
T 101, denotes a product available from Ethox Corporation which is a monoester/diester blend of isodecyl acid phosphate.
BIO-SOFT
T S-100 denotes a product available from Stepan Company which is a linear dodecylbenzene sulfonic acid.
STEPANTAN
T
M H-100, denotes a product available from Stepan Company which is a branched dodecylbenzene sulfonic acid.
PRIPOL
TM 1009, denotes a product available from Unichema International which is a C 36 dimer carboxylic acid.
MPEG 350 AC denotes a product available from The Dow Chemical Company which is an acetate ester of a 350 molecular weight methoxy polyethylene glycol monol.
GLY PO AC denotes a product available from The Dow Chemical Company which is a triacetate ester of a 1800 molecular weight propoxylated glycerin.
KESSCO
TM PEG 200 DL, denotes a product available from Stepan Company which is a dilaurate ester containing four moles of ethylene oxide.
PAPI
TM 27 denotes a product available from the Dow Chemical Company, which is a polymeric diphenylmethane diisocyanate having a 134 isocyanate equivalent weight.
PAPI
TM 88 denotes a product available from The Dow Chemical Company, which is a polymeric diphenylmethane diisocyanate having a 136 isocyanate equivalent weight.
ISONATE
TM 125M denotes a product available from The Dow Chemical Company, which is diphenylmethane diisocyanate having a 125 isocyanate equivalent weight WO 96/01293 PCT/US95/08333 Examples 1-6 Six different binder compositions (examples 1-6) of the present invention were prepared using the formulations shown in Table 1. Three additional binder compositions (controls 1, 3 and 4) were also prepared and did not contain any polyether containing compounds therefore, these do not represent embodiments of the present invention and are included for comparative purposes only.
Each formulation was run at a polyisocyanate: polyether:organic acid weight proportion of 100 parts:13.6 parts:9.9 parts, except for controls 1, 3 and 4 which were run at a polyisocyanate:organic acid ratio of 100 parts:9.9 parts. Control 2 contained only polyisocyanate. The polyisocyanate used for each of the examples and controls was PAPI M 88.
For these examples the organic acid containing compound (2) was blended with the polyether containing compound at room temperature prior to contact with the isocyanate The polyether containing compound was weighed into a beaker, the organic acid was weighed into the same beaker, and the two compounds were then stirred together for several minutes until a clear, homogenous blend was produced. This blend remained as a single phase for several weeks.
Using the formulations described in Table 1, at the proportions described previously, composite boards were prepared at 6.2 percent binder content, based upon the dry weight of standard aspen oriented strandboard wood flakes (typically 3 inch by 1 inch by 0.05 inch), in order to test releasability of the formulations.
The formulations were metered together and sent through a static mixer just prior to spray application to wood flakes. The wood particles were tumbled in a rotating drum and the spray was introduced at a rate of 1 to 5 grams per second through a port -21- WO 96/01293 PCT/US95/08333 in the drum. The spray application lasted for 1 to 3 minutes, and the wood flakes were allowed to tumble an additional 10 minutes.
Following application of the blended components, the wood flakes were handlaid together into either a 2 foot by 2 foot or a inch by 10 inch deckle box which was positioned on a steel caul.
The wood mat was then pressed with the steel caul on the bottom, using either a steel caul sheet on top or directly against the top press platen. Typical press parameters were employed, using a time of 3 minutes; a temperature of 190 0 C; and a pressure of 400-500 psi (2.75 MPa 3.44 MPa). The press surfaces were initially cleaned thoroughly, but the surface was not otherwise treated before or during the press run.
As used herein, "release" is defined to mean that the part being prepared did not need to be pried from surfaces and did not leave behind particles that had to be scraped from the surface before another part could be pressed thereon.
-22- WO 96/01293 WO 96/ 1293PCTIUS95/08333 Table 1 Example Ptehe Organic Acid Platen Composition No. of Numiber Releases Containing Compound (3) 1 DOWANOLTM 500 ETHFACTM P0-0 316 stainless top, 18+ steel bottom 2 P 425 ETHFACTM P0-0 316 stainless top, carbon steel bottom 3 400 ETHFACTM PD-0 316 stainless top, carbon steel bottom 4DOWANOLTM 500 ETHFACTM 101 316 stainless 2+ 500 STEPANTANTM H- carbon steel top, 4 100 410 stainless bottomI 6 DOWANOLTM 500 PRIPOLTM 1009 carbon steel top, 4 410 stainless bottom control 1 ETHFACTM PD-O 316 stainless0 control 2 316 stainless a control 3 STEPANTANTM H- carbon steel top, 0 100 410 stainless bottom control 4 PRIPOLTM 1009 carbon steel top, 0 410 stainless bottom All experiments were performed using aspen wood.
indicates not present.
indicates presumption that additional releases could be achieved, based on easy release of past part; however, experiment was terminated at this particular point.
Controls 1-4 are for comparative purposes only and do not represent an embodiment of the present invention.
-23- WO 96/01293 PCT/US95/08333 Example 7 A 3000 g (80.6 percent by weight) portion of PAPI T 27 was charged into a multin;cked reactor equipped with mechanical agitator and nitrogen purge. The polyisocyanate was heated to 80-85 0
C,
whereupon a 300 g (8.1 percent by weight) portion of ETHFAC M
L
was added over about 15 minutes with mild foaming ensuing. After approximately 30 minutes, 420 g (11.3 percent by weight) of MPEG 350 AC was introduced over a 12 minute time period and the reaction was maintained between 80-85 0 C for an additional 1.5 hour.
A single-phase, homogeneous liquid was obtained.
A 6 kg portion of pine flakes having an 8 percent moisture content was treated with an aerosol spray of a 300 g (5 percent) aliquot of binder and pressed into 10 inch by 10 inch boards as described in Examples 1-6. Release results are shown in Table 2.
Example 8 A 3000 g (80.6 percent by weight) portion of PAPI T M 27 was heated to 82 0 C; subsequently, 300 g (8.1 percent by weight) of
ETHFAC
TM 101 was added over a 17 minute period with mechanical agitation and nitrogen purge. Mild foaming ensued. The reaction was maintained for 30 minutes at 82 0 C, then 420 g (11.3 percent by weight) of GLY-PO AC was added during a 20 minute period. After an additional 1.5 hour at 80-83 0 C, the reaction mixture was cooled to room temperature, yielding a nomogeneous, single-phase liquid.
A 431 g aliquot (5.8 perc t resin) of this binder was applied to 6957 g of pine flakes at i percent moisture content using methods described above. A series of 10 inch by 10 inch composite boards was prepared with release results reported in Table 2.
-24- WO 96/01293 PCT/US95/08333 Example 9 A 5.7 g (25 percent by weight) portion of KESSCOTM PEG 200 DL was combined with 1.2 g (5 percent by weight) of ETHEAC T M PD-0.
The mixture was added to 16.4 g (70 percent by weight) of PAPI TM 88 and thoroughly mixed prior to application to the aspen wood flakes, which occurred within a few minutes of its preparation.
An 803 g portion of aspen flakes was treated w'ith 23.3 g (2.8 percent by weight) of binder as described in Examples 1-6.
Data for composite board release is shown in Table 2.
Example A mixture of 80 g (8.6 percent by weight) of ETHFAC T 101 and 110 g (11.8 percent by weight) DOWANOL T 500 was introduced into a 243 g (26 percent by weight) portion of ISONATE- M 125M which has been heated at 85 0 C under nitrogen purge. The introduction is carried out over a 45 minute period. The colorless MDI becume a golden yellow with foam evident after about 8 minutes into the addition period. The reaction mixture was maintained at 81-89 0 C for an additionc 1.75 hour, then allowed to cool, revealing a turbid yellow, somewhat viscous consistency. The mixture was then blended with 500 g of PAPI T 88 at ambient temperature.
A 340 g aliquot of this mixture was sprayed onto 6000 g of pine flakes at 15 percent moisture content, utilizing apparatus and procedures previcusly outlinecL. Composite boards measuring 20 inches by 20 inches were prepared, with release data provided in Table 2.
The comparative examples designated as controls 5, 6 and 7 are for comparative purposes only, and are not considered to represent embodiments of the present invention.
WO 96/01293 PCTIUS95/08333 Comparative Example: Control A 15.1 g (7 percent by weight) amount of ETHFAC T 101 was added to 200 g of PAPI TM 88, heated to 90 0 C under nitrogen, during a minute interval. The reaction was continued at 90 0 C for an additional 2 hours.
Boards measuring 6 inches by 6 inches were prepared as previously detailed by treating aspen flakes with binder in a ratio of 164 g wood to 3.3 g (2 percent by weight) of binder. Release results are shown in Table 2.
Comparative Example: Control 6 A 28.7 g portion of PAPI T 88 was combined with 9.6 g percent by weight) of MPEG 350 AC at ambient temperature. This mixture was applied to 1395 g of aspen flakes, representing 2.7 percent by weight. Release data for the composite boards formed is shown in Table 2.
Comparative Example: Control 7 A 5.7 g (25.8 percent by weight) amount of KESSCO TM PEG 200 DL was blended with 16.4 g of PAPI TM 88 and applied to 1083 g of aspen flakes, yielding 2 percent by weight. Release date for the composite boards is provided in Table 2.
-26- WO 96/01293 WO 96/ 129PCTJUS9S/08333 Table 2 Example No. Polyether organic Acid Platen Composition No. of ________Compound Re leases 7 MPEG 350 AC ETHFACTM 101 carbon steel top, 100+ stainless bottom______ 8 GLY-PO AC ETHFACTM 101 Carbon steel top, 12+ stainless bottom 9 KESSCOTM 200 DL ETHFACTM PD-0 Carbon steel top, 4+ stainless bottom 0OWANOLTM 500 ETIIFACTM 101 Carbon steel top, 3+ (prepotyrner) 316 stainless bottom ETHFACTM 102 Carbon steel top, 0 316 stainless bottom control MPEG 350 carbon steel top, 0 6 316 stainless bottom control KESSCOTM 200 Carbon steel top, 0 7 410 stainless bottom Examples?7, 8, an'I 10 and controls 5 and 6 were performed using pine wood.
Examples 9 and control 7 were perfoarmed using aspen wood.
indicates not present indicates presumption that additional releases could be achieved, based on easy release of last part; however, experiment was terminated at this particular point.
Controls 5-7 are for comparative purposes only and do not represent an embodiment of the present invention.
-27-
Claims (11)
1. A self-releasing binder composition prepared by contacting at least a polyisocyanate compound, a compound of one of the following formulae in an amount from about 1 to about parts per 100 parts by weight of the polyisocyanate compound: x 0 0 I 11 II RO p OH R C -"OH R S PR OH I II OR' 0 (II) wherein X is oxygen or sulfur, R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic, R' is R, H, or an acyl, carbamayl, phosphoryl or sulfonyl group; and a polyether containing compound, with the following provisos: (i) wherein the polyether containing compound lacks an active hydrogen, the polyether containing compound is present in an amount from about 1 to about 2000 parts per 100 parts by weight of the polyisocyanate; and (ii) wherein the polyether containing compound contains at least one active hydrogen, the polyether containing compound is present in an amount such that, for compounds of Formula I, the OH:NCO equivalency ratio is less than about 0.77:1.00; for compounds of Formula II, the OH:NCO equivalency ratio is less than about 0.25:1.00; and for compounds of Formula III, the OH:NCO equivalency ratio is less than about 0.10:1.00; under reaction conditions sufficient to form a binder composition.
2. A process for preparing a composite article comprising contacting substrate particles and a self-releasing binder composition prepared by contacting at least a polyisocyanate compound, a compound of one of the following formulae in an -28- i WO 96/01293 PCT/US95/08333 amount from about 1 to about 20 parts per 100 parts by weight of the polyisocyanate compound: x 0 0 I II II RO p OH R C OH R S "OH OR' 0 (II) (111) wherein X is oxygen or sulfur, R is hydrocarbyl or hydrocarbyl containing an ether or ester group, and may be cyclic, R' is R, H, or an acyl, carbamoyl, phosphoryl or sulfonyl group; a polyether containing compound, with the following provisos: (i) wherein the polyether containing compound lacks an active hydrogen, the polyether containing compound is present in an amount from about 1 to about 2000 parts per 100 parts by weight of the polyisocyanate; and (ii) wherein the polyether containing compound contains at least one active hydrogen, the polyether containing compound is present in an amount such that, for compounds of Formula I, the OH:NCO equivalency ratio is less than about 0.77:1.00; for compounds of Formula II, the OH:NCO equivalency ratio is less than about 0.25:1.00; and for compounds of Formula III, the OH:NCO equivalency ratio is less than about 0.10:1.00; and substrate particles; under reaction conditions sufficient to form a composite article.
3. The process of Claim 2 wherein and are contacted first to form a reactive mixture, and then the reactive mixture is contacted wath the substrate particles
4. The process of Claim 2 wherein and are into a liquid, storage-stable mixture by heating the polyisocyanate at a temperature from about 60 0 C to about 190cC; combining therewith, either simultaneously or sul equently, from -29- WO 96/01293 PCT/US95/08333 about 1 to about 20 parts, per 100 parts of polyisocyanate, each of and to form a reaction mixture; and maintaining the heating for a time such that substantially no phase separation occurs upon cooling the reaction mixture to ambient temperature. The process of Claim 2 wherein the Formula I compound is selected from the group consisting of acid phosphates; acid phosphate anhydrides; acid polyphosphates; and mixtures thereof.
6. The process of Claim 5 wherein the acid phosphate anhydrides are selected from the group consisting of o-monoacyl, carbamoyl, phosphoryl and sulfonyl derivatives of acid anhydrides, and mixtures thereof, and the acid polyphosphates are selected from the group consisting of branched polyphosphates, cyclometaphosphates and mixtures thereof.
7. The process of Claim 2 wherein the polyether containing compound is selected from the group consisting of an active hydrogen polyether containing compound selected from the group consisting of polyether polyols, polyether thiols, polyether amines, polyether polyester polyols, hydroxy polyether siloxanes, amino polyether siloxanes and mixtures thereof; an inert polyether containing compound selected from the group consisting of polyether esters, polyether ethers, polyether isocyanate prepolymers, polyether ketones, polyether aldehydes, polyether polyesters, polyether thiolates, polyether amides, polyether epoxides, polyether siloxanes and mixtures thereof; and mixtures thereof.
8. The process of Claim 2 wherein the polyisocyanate is selected from the group consisting of diphenylmethane diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene diisocyanate, a,a-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures thereof, polymeric toluene diisocyanate, triphenylmethane WO 96/01293 PCT/US95/08333 triisocyanates, 4,4'-diisocyanato-diphenyl ether, polymethylene polyphenyl polyisocyanates, and mixtures thereof.
9. The process of Claim 2 wherein the substrate particles are selected from the group consisting of cellulosics, lignocellulosics, polymers, metals, inorganic materials, and mixtures thereof. The process of Claim 2 wherein the Formula II compound is selected from carboxylic acids, dimer carboxylic acids, polycarboxylic acids and mixtures thereof, and the Formula III compound is selected from sulfonic acids, polysulfonic acids and mixtures thereof. -31- i INTERNATIONAL SEARCH REPORT Applicaton No PCT/US 95/08333 A. CLASSIFICATION OF SUBJECT MATTER IPC 6 C08L97/02 C08G18/70 //(C08L97/02,75:00) According to International Patent Clasfication (IPC) or to both national classificauon and IPC I B. FIELDS SEARCHED Mirimum documentation searched (classification system followed by classification symbols) IPC 6 C08L C08G Documentation searched other than rmnmum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the internatonal search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where appropnate, of the relevant passages Relevant to claim No. A US,A,4 382 108 CARROLL ET AL.) 3 May 1 1983 see claims 1-7,13-18 see column 2, line 35 line 47 see column 5, line 58 column 6, line 47 A US,A,4 257 995 MC.LAUGHLIN ET AL.) 24 1 March 1981 cited in the application see claims 1,8-14,20-24 see column 6, line 30 line 47 see column 7, line 15 line 67 A US,A,4 376 088 PRATHER) 8 March 1983 1 see claims 1,4,6,7,10 see column 4, line 5 column 5, line SFurther documents are listed in the continuation of box C. Patent family members are listed in annex. Specal categories of ated documents: *T later document published after the international filing date or priority date and not in conflict with the application but document defining the general state of the art which is not cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international X document of partcular relevance; the claimed invention filing drAe cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior t the interational filing date but in the art later than the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 18, 10 9 October 1995 18 Name and mailing address of the ISA Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rijswijk Tel. -70) 340.2040, T. 31 651 epo nI, Van Puymbroeck, M Fax: (+11.70) 340-3016 Form PCT/ISAI/10 (saiond isht) (July 1992) page 1 of 2 INTrl'IINATIONAL SEACH REPORT Ine.-o Application No PCT/US 95/08333 C.(Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT C 4 ory Ciation of documntr 14111 indication, where appropriate. of the relevant pamiges Relevant to claim No, A EP,A,0 019 859 (BAYER) 10 December 1980 1 see plaes 9,2lne146, in72 see page 19, line 11 line 31 see page 15, line 81 line US,A,4 528 153 cited in the application A EP,A,0 269 869 (JIM WALTER RESEARCH) 81 June 1988 see claims 1,2,5,8-10 see page 3, line 40 line 56 US,A,4 933 232 cited in the application Foms PCT/ISA/210 (continuation of second silwt) (July 1992) page 2 of 2 INTERNA7ONAL SEARCH REPORT F1t,..oX Application No PCT/US 95/08333 Patent document I Publication IPatent family I Publication cited In search report I date Imembcr(s) I dateI US-A-4382108 03-05-83 AU-B- 550125 06-03-86 AU-B- 9171182 30-06-83 CA-A- 1175999 09-10-84 EP-A,B 0082295 29-06-83 JP-C- 1454597 25-08-88 JP-A- 58110243 30-06-83 JP-B- 62060264 15-12-87 US-A-4257995 24-03-8 1 AT-B- 383132 25-05-87 AU-B- 534399 26-01-84 AU-B- 6386780 01-10-81 BE-A- 886014 04-05-81 CA-A- 1123817 18-05-82 CH-A- 652964 13- 12-85 FR-AB 2479087 02-10-81 GB-A,B 2072686 07-10-81 JP-C- 1414107 10-12-87 JP-A- 56137950 28-10-81 JP-B- 62023641 25-05-87 NL-A- 8100106 16-10-81 AU-B- 527595 10-03-83 AU-B- 5116479 03-04-80 CH-A- 648575 29-03-85 DE-A- 2932175 10-04-80 FR-A,B 2437292 25-04-80 GB-A,B 2031914 30-04-80 NL-A- 7906306 01-04-80 SE-B- 433855 18-06-84 SE-A- 7908062 30-03-80 US-A-4376088 08-03-83 NONE EP-A-0019859 10-12-80 DE-A- AT-T- AU-B- AU-B- CA-A- JP-B- JP-C- JP-A- 2921689 2795 534659 5886380 1150887 1013499 1529130 55160013
11-12-80
15-04-83 09-02-84 04-12-80
26-07-83 0)7-03-89 15-11-89 12-12-80 Formt PCT/ISA1310 (patent familY annex) (July 191n) page 1 of 2 MNERNATIONAL SEARCH REPORT F nn.)WAppcauon No 1, PCT/US 95/08333 Ps~ent document Pbcaion Patent family I Publicao cited in search report dacmember(s) T dame EP-A-0019859 US-A- 4478738 23-10-84 US-A- 4528153 09-07-85 US-A-4528153 09-07-85 OE-A- 2921689 11-12-80 AT-T- 2795 15-04-83 AU-B- 534659 09-02-84 AU-B- 5886380 04-12-80 CA-A- 1150887 26-07-83 EP-A,B 0019859 10-12-80 JP-B- 1013499 07-03-89 JP-C- 1529130 15-11-89 JP-A- 55160013 12-12-80 US-A- 4478738 23-10-84 EP-A-0269869 08-06-88 US-A- 4772442 20-09-88 US-A- 4933232 12-MG-90 US-A-4933232 12-06-90 US-A- 4772442 20-09-88 EP-A- 0269869 08-06-88 Forym PCTIISA/210 (Patant flunilY Ahnx) (JuY 1992) page 2 of 2
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27094494A | 1994-07-05 | 1994-07-05 | |
| US270944 | 1994-07-05 | ||
| US33316694A | 1994-10-02 | 1994-10-02 | |
| PCT/US1995/008333 WO1996001293A1 (en) | 1994-07-05 | 1995-06-30 | Self-releasing binder system for composite products |
| US333166 | 1999-06-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2915595A AU2915595A (en) | 1996-01-25 |
| AU679645B2 true AU679645B2 (en) | 1997-07-03 |
Family
ID=26954591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU29155/95A Expired - Fee Related AU679645B2 (en) | 1994-07-05 | 1995-06-30 | Self-releasing binder system for composite products |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0719303A1 (en) |
| JP (1) | JPH09502763A (en) |
| KR (1) | KR960704979A (en) |
| CN (1) | CN1131958A (en) |
| AU (1) | AU679645B2 (en) |
| BR (1) | BR9506013A (en) |
| CA (1) | CA2170397A1 (en) |
| FI (1) | FI960997A0 (en) |
| MY (1) | MY130593A (en) |
| NO (1) | NO960868L (en) |
| WO (1) | WO1996001293A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19724199A1 (en) * | 1997-06-09 | 1998-12-10 | Basf Ag | Emulsifiers |
| JP5634944B2 (en) * | 2011-06-02 | 2014-12-03 | 三井化学株式会社 | Polyurethane adhesive and laminate film |
| US9540513B2 (en) | 2012-11-21 | 2017-01-10 | Basf Se | Lignocellulosic article and method of producing same |
| WO2019068529A1 (en) * | 2017-10-06 | 2019-04-11 | Basf Se | Water-dispersible polyisocyanates |
| CN113103396B (en) * | 2020-01-13 | 2023-01-13 | 万华化学集团股份有限公司 | Artificial board without aldehyde addition and manufacturing method thereof |
| MX2022014103A (en) * | 2020-05-11 | 2022-12-08 | Huntsman Int Llc | A binder composition. |
| KR102515229B1 (en) * | 2023-01-26 | 2023-03-30 | 더본드 주식회사 | Urethane modified epoxy resin composition with improved adhesion and flexibility and construction method of thin polmer surface treatment pavement using the same |
| KR102755619B1 (en) * | 2024-07-29 | 2025-01-22 | 시원글로벌 주식회사 | Epoxy Paving Composition for Road Paving and Low-noise Drainage Paving Method using Thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4257995A (en) * | 1979-05-03 | 1981-03-24 | The Upjohn Company | Process for preparing particle board and polyisocyanate-phosphorus compound release agent composition therefor |
| DE2921689A1 (en) * | 1979-05-29 | 1980-12-11 | Bayer Ag | SELF-SEPARATING ISOCYANATE-BASED BINDERS AND THE USE THEREOF IN A METHOD FOR THE PRODUCTION OF MOLDED BODIES |
| US4376088A (en) * | 1981-03-18 | 1983-03-08 | The Upjohn Company | Process for preparing a particle board using a self-releasing binder comprising a polyisocyanate and a sulfur-containing release agent |
| US4382108A (en) * | 1981-12-21 | 1983-05-03 | The Upjohn Company | Novel compositions and process |
| US4772442A (en) * | 1986-11-28 | 1988-09-20 | Jim Walter Research Corp. | Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites |
| US4933232A (en) * | 1986-11-28 | 1990-06-12 | Jim Walter Research Corp. | Isocyanate-carboxyl group-containing fatty compounds for manufacture of lignocellulosic composites |
-
1995
- 1995-06-30 KR KR1019960701106A patent/KR960704979A/en not_active Application Discontinuation
- 1995-06-30 CN CN95190739A patent/CN1131958A/en active Pending
- 1995-06-30 AU AU29155/95A patent/AU679645B2/en not_active Expired - Fee Related
- 1995-06-30 EP EP95924769A patent/EP0719303A1/en not_active Withdrawn
- 1995-06-30 JP JP8503952A patent/JPH09502763A/en active Pending
- 1995-06-30 BR BR9506013A patent/BR9506013A/en not_active Application Discontinuation
- 1995-06-30 WO PCT/US1995/008333 patent/WO1996001293A1/en not_active Application Discontinuation
- 1995-06-30 CA CA002170397A patent/CA2170397A1/en not_active Abandoned
- 1995-07-05 MY MYPI95001874A patent/MY130593A/en unknown
-
1996
- 1996-03-04 NO NO960868A patent/NO960868L/en unknown
- 1996-03-04 FI FI960997A patent/FI960997A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1131958A (en) | 1996-09-25 |
| MY130593A (en) | 2007-07-31 |
| NO960868L (en) | 1996-05-03 |
| WO1996001293A1 (en) | 1996-01-18 |
| NO960868D0 (en) | 1996-03-04 |
| BR9506013A (en) | 1997-08-19 |
| JPH09502763A (en) | 1997-03-18 |
| FI960997A (en) | 1996-03-04 |
| KR960704979A (en) | 1996-10-09 |
| CA2170397A1 (en) | 1996-01-18 |
| AU2915595A (en) | 1996-01-25 |
| EP0719303A1 (en) | 1996-07-03 |
| FI960997A0 (en) | 1996-03-04 |
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