WO1998003568A1 - Thermosetting phenolic resin composition - Google Patents
Thermosetting phenolic resin composition Download PDFInfo
- Publication number
- WO1998003568A1 WO1998003568A1 PCT/US1997/012274 US9712274W WO9803568A1 WO 1998003568 A1 WO1998003568 A1 WO 1998003568A1 US 9712274 W US9712274 W US 9712274W WO 9803568 A1 WO9803568 A1 WO 9803568A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- radical
- resin
- nitrogen
- curing agent
- acidic phosphorus
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 17
- 239000005011 phenolic resin Substances 0.000 title claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 11
- 229920001187 thermosetting polymer Polymers 0.000 title description 4
- 229920005989 resin Polymers 0.000 claims abstract description 129
- 239000011347 resin Substances 0.000 claims abstract description 129
- 229920003987 resole Polymers 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- 230000002378 acidificating effect Effects 0.000 claims abstract description 56
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011342 resin composition Substances 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 176
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 89
- 229960003742 phenol Drugs 0.000 claims description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims description 52
- 239000011574 phosphorus Substances 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 43
- 239000003377 acid catalyst Substances 0.000 claims description 37
- -1 methylene phosphonic acid Chemical compound 0.000 claims description 32
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 22
- 125000004437 phosphorous atom Chemical group 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000002989 phenols Chemical class 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000000805 composite resin Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical group OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 6
- 125000002993 cycloalkylene group Chemical group 0.000 claims 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 2
- SGPGESCZOCHFCL-UHFFFAOYSA-N Tilisolol hydrochloride Chemical compound [Cl-].C1=CC=C2C(=O)N(C)C=C(OCC(O)C[NH2+]C(C)(C)C)C2=C1 SGPGESCZOCHFCL-UHFFFAOYSA-N 0.000 claims 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract description 5
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003018 phosphorus compounds Chemical class 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 65
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 150000003254 radicals Chemical class 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003607 modifier Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 0 CN(CP(O)(O)=O)*P(O)(O)=O Chemical compound CN(CP(O)(O)=O)*P(O)(O)=O 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- VTCDZPUMZAZMSB-UHFFFAOYSA-N 3,4,5-trimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1OC VTCDZPUMZAZMSB-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- MBGGFXOXUIDRJD-UHFFFAOYSA-N 4-Butoxyphenol Chemical compound CCCCOC1=CC=C(O)C=C1 MBGGFXOXUIDRJD-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910018828 PO3H2 Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 2
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012431 aqueous reaction media Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 238000009730 filament winding Methods 0.000 description 2
- 238000009787 hand lay-up Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 1
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- DECTVMOFPJKFOZ-UHFFFAOYSA-N 2,6-bis(hydroxymethyl)phenol Chemical compound OCC1=CC=CC(CO)=C1O DECTVMOFPJKFOZ-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- HRUHVKFKXJGKBQ-UHFFFAOYSA-N 3,5-dibutylphenol Chemical compound CCCCC1=CC(O)=CC(CCCC)=C1 HRUHVKFKXJGKBQ-UHFFFAOYSA-N 0.000 description 1
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- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
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- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- ILASIIGKRFKNQC-UHFFFAOYSA-N 4-methoxy-3-methylphenol Chemical compound COC1=CC=C(O)C=C1C ILASIIGKRFKNQC-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical group CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000001654 beetroot red Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
Definitions
- This invention relates to a phenolic resin composition capable of being thermally cured and having both a long pot life and a fast curing rate.
- a phenolic resole resin composition particularly relates to a phenolic resole resin composition and especially a phenol-formaldehyde resole resin composition containing a mixture of (a) a phenol- formaldehyde resole resin, and (b) a latent curing agent selected from a particular class of nitrogen-containing phosphorous compounds made from either phosphoric acid or
- the present invention is further directed to a method of making the phenolic resole resin composition, to a method of curing the phenolic resin composition and also to a method of making molded articles and composites using the phenolic resole resin composition.
- Phenolic resole resins have long been cured with strong acids, such as sulfuric
- V unacceptable extent, the ultimate cure rate of the resin at the elevated cure temperature.
- a latent catalyst comprising a salt of a primary or secondary amine and a strong acid.
- This latent catalyst improves storage stability (pot life) of the resole resin composition, while providing a cure rate at an elevated temperature comparable to the rate obtained using conventional strong acid catalysts.
- Strong acids also may be added to the composition, to an extent to act synergistically with the latent catalyst to accelerate the rate of reaction; but preferably not in an amount which would cure the
- U.S. Patent 5,378,793 (European Patent Application 539,098) represents another approach.
- This patent discloses using a partial phosphate ester as a hardener for phenolic resole resins.
- the partial phosphate ester is prepared by reacting (partially esterifying) condensed phosphoric acids, such as orthophosphoric acid, pyrophosphoric acid, tetraphosphoric acid or phosphorus pentoxide under relatively stringent conditions of temperature and vacuum, with polyols, such as glycerol,
- the hardener cures the resole relatively slowly at a lower temperature, but allows a rapid cure when the temperature is increased. This presumably is due to dissociation of the ester at an elevated temperature to release free acid which acts as the hardener
- the partial ester is stable (i.e., has a relatively low acid value) and does not contribute to a premature
- the present invention is directed to a phenolic resole resin composition capable
- the present invention is based upon the discovery that certain nitrogen-
- phosphorus compounds made from either phosphoric acid or phosphorous
- the nitrogen-containing acidic phosphorus latent curing agent hereinafter alternatively referred to as the nitrogen-containing acidic phosphorus latent curing agent, the acidic phosphorus curing agent or the latent curing agent, desireably alter the hardening behavior of phenolic resole resin compositions
- the invention is directed to the use of certain nitrogen-containing acidic phosphorus latent curing agent
- acidic phosphorus latent curing agents which are compounds containing one or more moieties of the following formula:
- R is selected from a Cj to C 6 alkylene radical, a C 3 to C 7 cycloalkylene radical, an arylene radical and a divalent radical of the formula:
- x and z are integers of 1 to 6, and y is an integer from 0 to 2 and wherein the divalent radical is bonded to the phosphorous atom of said moieties through the terminal oxygen atom of said radical.
- nitrogen-containing acidic phosphorus latent curing agents includes compounds of the following formula:
- R is selected from a to C 6 alkylene radical, a C 3 to C - cycloalkylene radical, an arylene radical and a divalent radical of the formula:
- x and z are integers of 1 to 6, and y is an integer from 0 to 2 and whereir ⁇ the divalent radical is bonded to the phosphorous atoms of said compound through the
- Another class of nitrogen-containing, acidic phosphorus curing latent agents includes compounds of the formula:
- R" is a divalent organic radical, such as an alkylene group having from 1 to 12 carbon atoms and R has the same meaning noted above.
- R is a divalent organic radical, such as an alkylene group having from 1 to 12 carbon atoms and R has the same meaning noted above.
- Yet another class of nitrogen-containing, acidic phosphorus latent curing agents has the formula:
- the present invention is directed to the use of a combination of such a nitrogen-containing, acidic phosphorus latent curing agent with
- a strong acid catalyst for use as the hardening agent of a phenolic resole resin composition.
- the latent curing agent and the strong acid catalyst are present in the phenolic resole resin composition in a sufficient amount, and in a suitable weight ratio, which does not prematurely cure the phenolic resole resin at a temperature below a desired elevated hardening temperature for the resin, but which causes a rapid hardening of the resin at the desired cure (hardening) temperature.
- resin compositions exhibit both a long pot life at below the curing temperature and a
- the present invention also is directed to a method of making a phenolic resole resin composition comprising reacting phenol with formaldehyde under alkaline conditions to form a phenolic resole resin, neutralizing the resin, adding a latent curing agent, and subsequently adding a strong acid catalyst, wherein the latent curing agent is added in a sufficient amount to retard the curing of the resin at a first lower temperature in the presence of the strong acid catalyst, but to permit a rapid cure at a second higher temperature.
- the present invention is further directed to a method of making a resin composite comprising impregnating a substrate with the resin composition and jthen curing (hardening) the composition at an elevated temperature.
- the substrate is impregnated at an ambient temperature to slightly above ambient temperature.
- the present invention is directed to a predominatly aqueous phenolic resole resin composition capable of being thermally cured, i.e., a thermosetting resin composition, comprising a mixture of (a) a phenolic resole resin, and (b) a nitrogen- containing acidic phosphorus latent curing agent containing one or more moieties of the following formula:
- R is selected from a to C 6 alkylene radical, a C 3 to C 7 cycloalkylene radical, an arylene radical and a divalent radical of the formula:
- x and z are integers of 1 to 6, and y is an integer from 0 to 2 and wherein the divalent radical is bonded to the phosphorous atom of said moieties through the
- agents includes compounds of the following formula:
- R is selected from a C t to C 6 alkylene radical, a C 3 to C 7 cycloalkylene radical, an arylene radical and a divalent radical of the formula:
- x and z are integers of 1 to 6, and y is an integer from 0 to 2 and whereir the divalent radical is bonded to the phosphorous atoms of said compound through the
- R is a divalent organic radical, such as an alkylene group having from 1 to 12 carbon atoms and R has the same meaning noted above.
- R is a divalent organic radical, such as an alkylene group having from 1 to 12 carbon atoms and R has the same meaning noted above.
- the present invention in directed to a phenolic resole resin composition capable of being thermally cured comprising a mixture of (a) a phenolic resole resin, (b) a latent curing agent as above described, and (c) a strong acid curing catalyst, wherein the latent curing agent is present in a sufficient amount relative to the strong acid to retard the curing (hardening) of the resin at a first lower temperature in the presence of the strong acid catalyst, but to permit a rapid cure at a second higher temperature.
- the phenolic resole resin may be prepared in a known manner from well known starting materials. Such resins are prepared by reacting, under alkaline conditions, an
- suitable phenolic resole resins may be produced by reacting formaldehyde and a phenol component in an aqueous reaction medium under the alkaline reaction condition.
- An alkaline reaction condition can be established by use of any of the wide variety of basic catalysts, organic and inorganic, known to those skilled in the art.
- an alkali metal hydroxide, and usually sodium hydroxide is often the catalyst of choice
- amine catalysts are also preferred.
- the phenolic resole resin preferably is prepared so that it contains a large
- the resin contains a large proportion of the tetramethylolated phenolic species or tetradir ⁇ ers, e.g., 4 to 8 wt% of the resin.
- the methylol groups are capable of reacting with one another at elevated temperatures with or without the addition of auxiliary catalysts. Such resins can cure under the influence of both basic and acidic catalysts.
- the present invention is directed to curing (hardening) the resin in the presence of an acid catalyst.
- Suitable phenolic resole resins for use in the present invention are prepared
- a mole ratio of formaldehyde to phenol preferably of at least about 0.9: 1, and more preferably at least about 1:1, up to a mole ratio of about 3.5: 1 and more preferably up to about 1.85: 1.
- Particularly useful phenolic resole resins in the present invention exhibit a long pot life and a lower tendency to show strong exotherms of the
- the phenol component used to prepare the phenolic resole resin includes any phenol typically used in preparing phenolic resole resins, which are not substituted at either the two ortho positions or at one ortho and the para position, such unsubstituted positions being necessary for the desired polymerization (dimerization, trimerization, etc.) reactions to occur. Phenols substituted in these positions may be used in lesser quantities (e.g., up to about 30 weight %, and generally not more than about 10 weight %, of the phenol component) as it is known in the art to control molecular weight by a chain termination reaction. Any one, all, or none of the remaining carbon atoms of the phenol ring can be substituted in a conventional fashion.
- substituents can vary widely, and it is only necessary that the substituent not interfere in the polymerization of the aldehyde with the phenol at the ortho and/or para positions thereof.
- at least a portion of the phenol component must include a phenol not blocked at either of the ortho and the para positions (i.e., a trifunctional phenol) so that the resin is thermosettable.
- a trifunctional phenol a phenol not blocked at either of the ortho and the para positions
- at least 10% by weight of the phenol component should include such tri-functional phenols, more preferably at least 25% by weight, most preferably at least 75% by weight and usually the phenol component consists essentially entirely of such tri-functional phenol.
- Substituted phenols employed in the formation of the phenolic resins include, for example, alkyl substituted phenols, aryl substituted phenols, aralkyl substituted phenols, cycloalkyl substituted phenols, alkenyl-substituted phenols, alkoxy substituted phenols, aryloxy substituted phenols, and halogen-substituted phenols, the foregoing substituents possibly containing from 1 to 26, and preferably from 1 to 9, carbon
- Suitable phenols for preparing the resole resin composition of the present invention include: hydroxybenzene (phenol), o-cresol, m-cresol, p- cresol, 3,5-xylenol, 3,4-xylenol, 3,4,5-trimethylphenol, 3-ethyl phenol, 3,5-diethyl
- phenol p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, phenylethyl, 3,5- dimethoxy phenol, 3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3- methyl-4-methoxy phenol, p-phenoxy phenol and mixtures thereof.
- Ordinary phenol normally is preferred for most applications.
- the phenol component may also include a small amount of di-functional phenol such as resorcinol, catechol, or hydroquinone or p.p'-dihydroxy bi-phenyl.
- Formaldehyde can be used alone or in combination with any of the aldehydes or their equivalents heretofore employed in the formation of phenolic resold .esins
- aldehydes including, for example, acetaldehyde, propionaldehyde, butylaldehyde furfuraldehyde, and benzaldehyde.
- the aldehydes employed have the formula R'CHO wherein R' is a hydrogen or hydrocarbon radical generally of 1 -8 carbon atoms.
- R' is a hydrogen or hydrocarbon radical generally of 1 -8 carbon atoms.
- some aldehydes e.g., acetaldehyde and butylaldehyde, improve toughness of the resole resin at the expense of lowering the HDT thereof (heat distortion temperatures, as determined by American Society for Testing and Materials ASTM D-648).
- difimctional aldehydes can be used to prepare the phenolic resin, and could advantageously be used to introduce cross-links
- Formaldehyde can be supplied in any one of its commonly available forms including formalin solutions and paraformaldehyde.
- the phenolic resole resin can be prepared in the presence of other resin modifier monomers such as urea, furan and melamine. It is intended that such modified phenolic resins be included in the thermosetting phenolic resole resin compositions of the present invention.
- the resole resin composition of the present invention preferably has a solids
- the viscosity of the composition is usually from about 200 cp to 5000 cp, and preferably about 300 to 1500 cp, measured at 25 °C. As with solids content, both higher and lower viscosities may be used depending on specific applications.
- the composition preferably has a)free phenol content below 15% by weight and a free aldehyde content below 3% by weight, more preferably below 1.0% by weight, based on the weight of the resin composition.
- the phenolic resole resin can be treated with an aldehyde scavenger to lower the amount of free aldehyde in the resin.
- the scavenger is added in amounts sufficient to reduce the level of free aldehyde without significantly affecting the cure rate or desirable strength of the cured resin. It is preferred to use between 0.5 and 1.5 mole equivalents of scavenger per mole of free aldehyde present at the end of the resole preparation.
- Typical aldehyde (formaldehyde) scavengers include urea, melamine, toluene sulfonamide and dicyandiamide.
- Preferable scavengers are urea and toluene
- modifiers include, for example, chain terminating phenols, glycols, with or without halogen substitution for additional fire retardancy, polyester polyols, polyether polyols, alkyl phenols, hydroxy- containing acrylates, and the like and mixtures thereof.
- the proportion of such modifiers incorporated into the resole resin composition typically ranges from 5 to 35
- modifiers such as fire retardants and fillers can be added to complete the phenolic resole resin composition.
- Reactive modifiers can be added to the resole resin after it has been formulated such as di- and higher polyols, e.g., di- or polyhydric phenols, resorcinol, phloroglucinol, and the like.
- modifiers to achieve special effects in particular applications may be appropriate, e.g., polyvinyl butyrals, or epoxies for better impact strength in composites.
- Another component which may be used in phenolic resole resin compositions of the present invention is an organic solvent. While the resin composition is predominately aqueous, a variety of organic solvents can be used in diluting the phenolic resole resin composition to a desired solids concentration or viscosity for
- Suitable organic solvents include aromatic solvents including benzene, toluene, xylene, ethyl benzene, and the like, polar solvents such as furfural, furfuryi alcohol (which co-reacts under acid conditions) various Cellosolves, carbitols,
- the other essential component of the phenolic resole resin composition of the invention is a nitrogen-containing acidic phosphorus latent curing agent which is a
- R is selected from a C x to C ⁇ alkylene radical, a C 3 to C 7 cycloalkylene radical, an arylene radical and a divalent radical of the formula:
- the latent curing agent generally is provided in the composition in an amount between about 0.5 to 20 parts per hundred parts of the phenolic resole resin solids (pphr), and more preferably between about 1 to 10 pphr. Most often, the latent acidic phosphorus curing agent will be employed in an amount of between about 1 and 7 parts per hundred parts of the phenolic resole resin solids
- latent curing agents can be prepared by reacting (partially neutralizing) oithophosphoric acid (H 3 PO 4 ) with a di- or tri-alkanol amine.
- Suitable alkanol amines may have the formula:
- R' is selected from hydrogen, a C, to C 6 alkyl, C, to C 6 alkoxy,
- a cycloalkyl and an aryl, x and z are integers of 1 to 6, y is an integer from 0 to 2.
- Phosphoric acid equivalents such as pyrophosphoric acid (which is equivalent to 105% orthophophoric acid), tetraphosphoric acid (which is equivalent to 115%
- oithophosphoric acid or phosphorus pentoxide (which is equivalent to 138% orthophosphoric acid) also may be used as the phosphoric acid source.
- alkanol amines are commercially available and include dimethanol- amine, diethanolamine, dipropanolamine, dibutanolamine, trimethanolamine, triethanolamine,
- tripropanolamine, tributanolamine and the alkylene oxide adducts of these alkanolamines such as the ethylene oxide and propylene oxide adducts.
- Acidic phosphorus curing agents prepared in this manner have the following formula. 0
- a particularly preferred latent curing agent is the one prepared by neutralizing ortho-phosphoric acid with trimethanolamine, triethanolamine, tripropanolamine and the like. These preferred curing agents have the formula:
- n is an integer of 1 to 4.
- the neutralization adduct of triethanolamine (TEA) and phosphoric acid in an amount of three moles of acid per mole of TEA is known in the art and is commercially
- ATP is available commercially from P. Chem, Inc., Latexo, Texas.
- the reaction product is basically
- ATP has the following formula. o
- a second class of acidic phosphorus latent curing agents can be prepared by reacting phosphorous acid, formaldehyde and
- Hydrochloric acid may be added to the reaction mixture to suppress the oxidation of phosphite to phosphate.
- R' is a monovalent organic radical, preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms such as propyl, isopropyl, butyl, hexyl or 2-
- hydroxyethyl can be prepared from a primary amine.
- An example of a tri-phosphonic acid is aminotris(methylene-phosphonic acid) (ATMP) made by reacting ammonia, formaldehyde and phosphorous acid.
- ATMP has the formula:
- ATMP also is commercially available from P. Chem, Inc.
- tetra- phosphonic acids R(PO 3 H 2 ) 4 are the alkylene diamine tetra(methylene-phosphonic acids) of the formula (VII):
- R" is a divalent organic radical, such as an alkylene group having from 1 to 12 carbon atoms, and R is as defined above.
- R is ethylene diamine tetra(methylene phosphonic acid).
- pentaphosphonic acids, R(PO 3 H 2 ) 5 are examples of
- dialkylene triamine penta(methylene phosphonic acids) of the formula (VIII):
- such pentaphosphonic acids include diethylene triamine penta(methylene phosphonic acid) of the formula:
- the nitrogen-containing acidic phosphorus latent curing agent used in accordance with the present invention may be used as the sole hardening agent, or more usually is used in combination with conventional acid hardeners, or acid catalysts.
- Acid catalysts for use in the phenolic resole resin composition of the present inventions are conventional strong acid catalysts known in the art.
- Such acids include inorganic acids such as hydrochloric, sulfuric, and phosphoric acid, and organic acids such as trichloracetic, sulfamic, aromatic di- and polysulfonic, e.g., phenyl sulfonic and other organo-sulfonic acids, conventional latent strong acid catalysts such as acid chlorides, and mixtures thereof.
- Preferred strong acid catalysts include a mixture of phosphoric acid and a strong organo-sulfonic acid such as the commercially available mixture of toluene and xylene sulfonic acids provided in ethylene glycol solvent or methane sulfonic acid.
- the strong acid catalyst is present in the phenolic resole resin composition in
- the strong acid catalyst is provided in the composition in an amount between about 0.5 to 20 parts per hundred parts of the phenolic resole resin solids (pphr), and more preferably between about 1 to 10 pphr.
- the strong acid catalyst may be provided in the phenolic resole resin composition in an amount from about 5% to about 80% by weight of the combination of the latent curing agent and strong acid catalyst, more usually in an amount from 25% to 60% by weight.
- an aromatic sulfonic acid such as p-toluene sulfonic acid (pTSA) is used as the add catalyst.
- pTSA p-toluene sulfonic acid
- low to ambient temperatures typically can be considered as less than 40 ° C, and preferably between about 0 ° C and 35 ° C, and
- the present invention also is directed to a method of making a fast curing, long pot life phenolic resin composition.
- a phenolic resin is first prepared from formaldehyde and phenol.
- a resin predominantly having the preferred highly methylolated spedes is prepared using a two-step process.
- phenol is reacted with formaldehyde in an aqueous reaction medium under
- the amount of alkaline catalyst is preferably between about 0.6 to 1.4 part by weight per 100 parts by weight of total phenol added.
- the caustic solution is usually of approximately 50% strength.
- the catalyst is added in approximately the same proportion as the phenol. For example, if 50% of the phenol is initially added, then 50% of the total catalyst charge is initially added.
- the full complement of formaldehyde is slowly added to drive the reaction to form the tetradimer.
- Adding the rernaining phenol and alkaline catalyst consumes residual unreacted formaldehyde and causes a lowering of the resin's viscosity.
- the resulting resin can be characterized as a bimodal distribution of methylolated species with a large fraction of highly methylolated dimers and another significant fraction of predominately monomethyiolated phenolic monomers.
- the bimodal distribution minimizes the level of 2,6 dimethylolphenol which is a highly reactive and undesirable species.
- the low level of this resin spedes results in the resin having better pot life and a lower tendency to show strong exotherms of the type which initiate at 55 °C.
- Alkaline reaction conditions can be established by use of any of the wide variety of alkaline catalysts, organic and inorganic, known to those skilled in the art.
- an alkali metal hydroxide is preferred such as sodium, lithium or potassium hydroxide.
- Sodium hydroxide is particularly preferred.
- catalysts include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide, aqueous ammonia and amines.
- alkaline catalyst promotes the reaction of the formaldehyde with phenol to form a phenol-formaldehyde issoie resin.
- the resin may then be neutralized as needed, for example, so as to obtain better
- acidic neutralizing agents can be used including, but not limited to, methane sulfonic, hydrochloric, phosphoric, and sulfuric acids.
- acidic latent curing agents also can be used to neutralize the resin, including for example, the nitrogen-containing acidic phosphorus latent curing agents of this
- a suffident amount of the neutralizing agent is added to establish a pH of between about 6.5 and 7.5 in the aqueous resin, although final pH levels as low as 4.0 often may also
- a nitrogen-containing acidic phosphorus latent curing agent then is added to the resia
- the nitrogen-containing acidic phosphorus latent curing agent can be used as the sole curing agent; but preferably is used in combination with a conventional strong add curing agent. In particular, it is preferred to use a relative amount of these two components so as to obtain a desired combination of extended pot life and rapid cure.
- the latent curing agent typically will be added in a sufficient amount to retard curing of the resin in the presence of a strong acid catalyst at low to ambient temperatures.
- a mixture of the latent curing agent and the strong acid catalyst is added to the resin immediately prior to resin use.
- the present invention also is directed to a method of making a resin composite using the phenolic resin composition.
- a composite is formed by impregnating a substrate with the resin composition comprising a mixture of (a) a phenolic resole resin, (b) a nitrogen-containing acidic phosphorus latent curing agent, and (c) a strong acid curing catalyst, wherein the latent curing agent is present in a sufficient amount to retard the curing of the resin in the presence of the strong acid catalyst at low to ambient temperatures.
- the temperature of the resin impregnated substrate is raised to an elevated temperature to cure the resin.
- the temperature is raised to a temperature above about 60 °C, and usually between about 65 C C to 85 °C.
- Composites can be cured overnight at temperatures as
- the resin composition of the present invention is suitable for hand layup and continuous laminating processes, for producing prepregs, for resin transfer molding (RTM), for ram injection molding, for pultrusion applications, for filament winding and for making sheet molding compound.
- RTM resin transfer molding
- ram injection molding for pultrusion applications
- filament winding for making sheet molding compound.
- fiberglass reinforcement one can use chopped strand glass mats that are currently used in preparing polyester hand lay-up composite products and phenolic-compatable glass such as CertainTeed RO9 Type 625 or PPG Hybon*. The equipment used for the manufacture of such reinforced
- composites is well known to those knowledgeable in this technology and in many cases basically comprises an impregnation tank containing the phenolic resole tesin composition of the invention.
- the reinforcing agent such as glass fibers, glass fiber roving or glass fabric is immersed in the tank to impregnate the
- the fibers may be wound on a mandrel (filament winding) or pulled through a die (pultrusion) to produce the desired composite shape.
- Method for assessing cure speed in a catalyzed resole at elevated temperature A 1 gram quantity of catalyzed resole is placed on a constant temperature hot plate with a surface temperature of 90 °C. The resin is cast in the form of a pancake 1.5 to 2.5 mm thick. As cure proceeds, the resin sample becomes opaque and at gel, enters into a rubber-like state. As cure proceeds, the viscosity increases as the sample becomes increasingly harder. The cure speed is assessed by measuring the time until the resin forms a solid mass, indicated by a failure of the resin to form strings as it is deformed.
- a catalyzed resin mixture (resin composition) is placed into a two ounce bottle.
- the viscosity of the sample is measured using a LVF Brookfield Viscometer and temperature is monitored using a thermocouple.
- the viscosity is measured as a function of time.
- the pot life is assessed as a function of the time for the sample to reach a viscosity of 3000 cp.
- Example 1 The following standard phenolic resole resins: GP 5022 (Resin A), GP 441T62
- the catalyst comprised a mixture of 77 pbw of ATP solids and 23 pbw of toluene/xylene sulfonic acid (TX) solids.
- TX toluene/xylene sulfonic acid
- Resin A was formulated with various amounts of a latent curing catalyst/strong
- the catalyst mixture was prepared from about 60 pbw of ATMP solids and 40 pbw of a blend of TX acid (Witco Witcat TX acid) and ethylene glycol (EG) solids having a TX.EG weight ratio of 42:58) The results are reported in Table 3 below As a control, Resin A was mixed with 5 phpr of the same TX and ethylene glycol (EG) mixture as the curing catalyst (as noted the TX and EG mixture had a TX:EG weight
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97934153A EP0914361B1 (en) | 1996-07-23 | 1997-07-15 | Thermosetting phenolic resin composition |
CA002260987A CA2260987C (en) | 1996-07-23 | 1997-07-15 | Thermosetting phenolic resin composition |
DE69701807T DE69701807T2 (en) | 1996-07-23 | 1997-07-15 | HEAT-CURING PHENOLIC RESIN COMPOSITION |
AU37277/97A AU3727797A (en) | 1996-07-23 | 1997-07-15 | Thermosetting phenolic resin composition |
AT97934153T ATE192169T1 (en) | 1996-07-23 | 1997-07-15 | HOME CURING PHENOLIC RESIN COMPOSITION |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/681,681 US5864003A (en) | 1996-07-23 | 1996-07-23 | Thermosetting phenolic resin composition |
US08/681,681 | 1996-07-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998003568A1 true WO1998003568A1 (en) | 1998-01-29 |
Family
ID=24736303
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/012274 WO1998003568A1 (en) | 1996-07-23 | 1997-07-15 | Thermosetting phenolic resin composition |
Country Status (8)
Country | Link |
---|---|
US (1) | US5864003A (en) |
EP (1) | EP0914361B1 (en) |
AT (1) | ATE192169T1 (en) |
AU (1) | AU3727797A (en) |
CA (1) | CA2260987C (en) |
DE (1) | DE69701807T2 (en) |
ES (1) | ES2146111T3 (en) |
WO (1) | WO1998003568A1 (en) |
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US7910109B2 (en) | 2002-02-13 | 2011-03-22 | Oxford Biomedica (Uk) Ltd. | MHC class II epitopes of 5T4 antigen |
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Also Published As
Publication number | Publication date |
---|---|
AU3727797A (en) | 1998-02-10 |
ES2146111T3 (en) | 2000-07-16 |
DE69701807T2 (en) | 2000-12-28 |
US5864003A (en) | 1999-01-26 |
EP0914361B1 (en) | 2000-04-26 |
CA2260987A1 (en) | 1998-01-29 |
EP0914361A1 (en) | 1999-05-12 |
ATE192169T1 (en) | 2000-05-15 |
CA2260987C (en) | 2004-10-05 |
DE69701807D1 (en) | 2000-05-31 |
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