USRE28495E - Poly(hexasubstituted melamines) - Google Patents
Poly(hexasubstituted melamines) Download PDFInfo
- Publication number
- USRE28495E USRE28495E US47691174A USRE28495E US RE28495 E USRE28495 E US RE28495E US 47691174 A US47691174 A US 47691174A US RE28495 E USRE28495 E US RE28495E
- Authority
- US
- United States
- Prior art keywords
- polymer according
- hexasubstituted
- bis
- poly
- formula
- 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
Links
- -1 Poly(hexasubstituted melamines) Polymers 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011968 lewis acid catalyst Substances 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 150000007974 melamines Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 125000000217 alkyl group Chemical group 0.000 abstract description 12
- 239000002841 Lewis acid Substances 0.000 abstract description 8
- 150000007517 lewis acids Chemical class 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 10
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001912 cyanamides Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229920000580 poly(melamine) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 description 1
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 1
- VQHXKRGSWGMXST-UHFFFAOYSA-N 1-[cyano(ethyl)amino]propan-2-yl-ethylcyanamide Chemical compound CCN(C#N)CC(C)N(CC)C#N VQHXKRGSWGMXST-UHFFFAOYSA-N 0.000 description 1
- MHFDBHXUHAGYIC-UHFFFAOYSA-N 2-(4-chloro-n-cyanoanilino)ethyl-(4-chlorophenyl)cyanamide Chemical compound C1=CC(Cl)=CC=C1N(C#N)CCN(C#N)C1=CC=C(Cl)C=C1 MHFDBHXUHAGYIC-UHFFFAOYSA-N 0.000 description 1
- 125000003858 2-ethylbutoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])O*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005979 2-naphthyloxy group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OXEZLYIDQPBCBB-UHFFFAOYSA-N 4-(3-piperidin-4-ylpropyl)piperidine Chemical compound C1CNCCC1CCCC1CCNCC1 OXEZLYIDQPBCBB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100264195 Caenorhabditis elegans app-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical group [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- NSBLIUUCSWIBRD-UHFFFAOYSA-N benzyl-[1-[benzyl(cyano)amino]propan-2-yl]cyanamide Chemical compound C=1C=CC=CC=1CN(C#N)C(C)CN(C#N)CC1=CC=CC=C1 NSBLIUUCSWIBRD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- QKHLYSXCJSDGJY-UHFFFAOYSA-N butyl-[12-[butyl(cyano)amino]dodecyl]cyanamide Chemical compound CCCCN(C#N)CCCCCCCCCCCCN(C#N)CCCC QKHLYSXCJSDGJY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
Definitions
- ABSTRACT Poly(hexasubstituted melamines) prepared by the Lewis acid catalyzed polymerization of alkylene bis- (N-substituted cyanamides) of the formula wherein R and R are broadly alkyl or aryl and R is alkylene. such polymers being curable to a storable B-stage as well as fully cured condition. having excellent high temperature stability and being useful as structural adhesives or binders.
- This invention relates to high temperature stable polymers, and more particularly to high temperature stable polymers prepared from alkylene bis-(N- substituted cyanamides).
- the polymers of this invention contain melamine (triamino-s-triazine) segments in which each of the amine hydrogens has been replaced by an organic group, and these segments are linked by alkylene groups.
- Polymers containing melamine segments have been prepared before.
- polymers containing triarylamino-s-triazine residues which are prepared by the reaction of trihalo-s-triazines with diamines, the reaction taking place with the liberation of hydrogen halide.
- the polymers retain a hydrogen atom on each of the amine groups present on each of the triazine segments, hence the polymer has a limited thermal stability.
- Polymers containing melamine segments in which all of the hydrogens of each of the amine groups present on each of the triazine segments of the polymer have been replaced by an organic group are described in US. Pat. Nos. 3,382,221 and 3,277,065. These polymers, however, are prepared by the free radical catalyzed polymerization of hexasubstituted melamines wherein at least four of the substituents are allyl groups, and polymerization takes place via addition reaction at the allylic double bond. Moreover, polymers described in these patents must be prepared in an inert atmosphere because the presence of oxygen in more than trace amounts inhibits the polymerization.
- Polymers containing melamine segments have also been prepared by polymerization of organic biscyanamides.
- alkylenedicyanamides may be polymerized by keeping them, with or without a basic accelerator, in a liquid state at an appropriate temperature.
- US. Pat. No. 3.303.101 describes the preparation of copolymers by heating a mixture of monocyanamides and dicyanamides. According to the disclosure of Smolin and Rapoport, "The Chemistry of Heterocyclic Compounds.” lnterscience. New York. 1959.2 page 357. the polymers described in these patents most likely contain iso-melamine segments.
- the present invention provides novel thermosetting poly(hexasubstituted melamines) that are readily prepared by the Lewis acid catalyzed polymerization of correspondingly substituted bis (Nsubstituted cyanamides), a process that does not require condensation with elimination of volatile by-products, does not require an inert atmosphere, does not involve the use of electronegative group-activated compounds, nor the use of free radical-generating catalysts or copolymerization with compounds containing active hydrogen, hydroxyl or thiol groups. Moreover, such poly(hexasubstituted melamines) possess good high temperature stability.
- an object of the present invention to provide poly(hexasubstituted melamines) having useful high temperature stability and excellent dielectric properties.
- lower alkyl and lower alkoxy embrace both straight and branched chain alkyl and alkoxy radicals. respectively. containing from I to 6 carbon atoms. for example, but without limitation thereto, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl. sec-pentyl. n-hexyl. 2-ethylbutyl.
- cyclo-lower alkyl embraces lower alkyl-substituted and unsubstituted cycloalkyl radicals containing a total of from 3 to 9 carbon atoms. including, when substituted.
- cyclopropyl for example, but without limitation thereto, cyclopropyl, cyclobutyl, methylcyclopropyl, cyclopentyl. ethylcyclopropyl. dimethylcyclopropyl. Z-methylcyclobutyl. 3-ethylcyclopropyl. 2.3-dimethylcyclobutyl. 2-ethylcyclobutyl. 3- ethylcyclobutyl. cycloheptyl. 2.3-diethylcyclopropyl. 2-methyl-3-ethylcyclopropyl. 2.3.4-trimethylcyclobu tyl.
- aryl embraces both substituted and unsubstituted monovalent organic radicals derived from aromatic hydrocarbons by the removal of one hydrogen atom, for example, but without limitation 3 thereto. phenyl. naphthyl. anthryl. pyridyl. carbazyl. indolyl. Z-triazinyl. furyl. benzoxazolyl. benzthiazolyl and the like. such radicals. if desired. optionally bearing one or more lower alkyl. lower alkoxy. aryl. halogen. carbo-lower alkoxy.
- arylsulfonyl or nitro substituents' embraces substituted or unsubstituted aryloxy radicals. for example. but without limitation thereto. phenoxy. Imaphthyloxy. 2- naphthyloxy. lanthryloxy.Z-anthryloxy.9-anthryloxy and the like. such radicals. if desired, optionally bearing one or more lower alkyl, lower alkoxy. aryl. halogen, carbo-lower alkoxy.
- alkylene embraces both straight and branched chain alkylene radicals of the formula C I-[ wherein n is an integer of from I to and the term halogen" includes chloro and fluoro.
- the poly(hexasubstituted melamines) of the present invention consist essentially of segments (repeating units) having the structural formula together with the two nitrogen atoms to which they are attached form a divalent radical of the formula
- the materials are oligomeric and thermoplastic. They apparently contain a mixture of trimeric to hexameric chains of starting dicyanamides. which do not have more than about two triazine rings in any one polymer chain. Their average molecular weight in the B stage is from about 300 to 3.000. At this stage they retain useful solubility in chlorinated hydrocarbon such as methylene chloride. chloroform and the like.
- the poly( hexasubstituted melamine) final product is prepared by heating. in the presence of a Lewis acid catalyst.
- the alkylene bis-(Nsubstituted cyanamides) that may be used to prepare the poly(hexasubstituted melamines) according to the present invention are bis- (N-alkylcyanamides). such as. for example. ethylene bislN-methylcyanamide).
- alkylene bis-[N-(substituted aryl) cyanamides] such as. for example, ethylene bis-[N-(4-chlorophenyl) cyanamide], butylene bis-[N-(methoxy phenyl) cyanamide] and butylene bis[l ⁇ l(4-phenoxyphenyl) cyanamide].
- alkylene bis-(N-substituted cyanamide) starting materials are prepared by known'procedures described in the literature. including. for example, the dehydration of bis-ureas as described by Robinson. Can. J. Chem. 32. 32, 901 (1954); the dehydration of thioureas as described by Kurzer. J. Chem. Soc. l950, 3269 and the preparation of l.4-dicyanopiperazine as described by Kramer. Chem. explicat. l9l0 l. 1532 and Franchimont and Kramer, Rec. trav. chem. 3l. 64 (1912).
- the poly(hexasubstituted melamines) of the present invention are prepared by heating one or more alkylene bis-(N-substituted cyanamides) with a Lewis acid catalyst.
- the temperature and time of heating are varied according to the amount of and nature of the Lewis acid catalyst chosen to effect the polymerization. Generally. temperatures range from about to 350 C. and polymerization times from about one hour to about 48 hours. and from about 0.5 to about 15 weight percent of Lewis acid catalyst is used. The higher the tempera ture and the greater the amount of catalyst used. the less is the time required to reach the B-stage and the thermoset stage of the polymer.
- the preferred conditions for preparing the poly(hexasubstituted melamines) are to heat the alkylene bis-(N-substituted cyanamides) at a temperature from 200 to 250 C. for from about two to 24 hours in the presence of l to 5 weight percent of a Lewis acid catalyst.
- the polymerization reaction is readily controlled. For any given amount of catalyst. the polymerization proceeds with controlled application of heat to the B- stage. where the polymers formed are soluble and thermoplastic. or is carried on to the thermoset stage. where the polymers are crosslinked and therefore insoluble. By discontinuing heating at the B-stage. regardless of whether a high or low percentage of catalyst is employed in the polymerization. the polymerization can be halted. At this stage the polymer may be stored at lower temperature for an essentially unlimited period of time and. when desired. converted to the thermoset stage simply by the application of heat.
- Lewis acid that may be used as catalyst for the polymerization of the alkylene bisJN-substituted cyanamides
- Suitable Lewis acids are selected from the hard and intermediate Lewis acids as classified by Pearson, J. Am. Chem. Soc.
- 85, 3633 and include but are not limited to aluminum chloride, aluminum bromide, aluminum iodide, stannic chloride, antimony trichloride, indium trichloride, cobaltic chloride, cobaltic bromide, indium oxide, cobaltic oxide, ferric oxide, ferric chloride, manganic acetate, manganic acetylacetonate, manganous acetylacetonate, titanium tetrachloride, titanium dioxide, boron trifluoride, boron trifluoride etherate, boron trichloride, ferrous chloride, cobaltus chloride, nickel chloride, manganese, dioxide, zinc chloride, lead chloride, lead iodide and the like. Some of these materials are of low activity and are essentially fillers. When used they may require the addition of more active catalyst to achieve complete cure within a practical length of time.
- the preferred Lewis acid catalysts are those that have a low volatility, such as, for example, Lewis acids that do not volatilize or decompose below about 200 C., and particularly indium trichloride or zinc chloride and the like.
- the polymerization of the alkylene organic bis-(N- substituted cyanamides) according to the present invention may be carried out in the presence of volatile Lewis acid catalysts; however, with such catalysts it is necessary that pressure equipment be utilized during the polymerization to confine the catalyst.
- the preferred catalysts are indium trichloride, stannic chloride, antimony trichloride, cobaltic chloride, zinc chloride, ferric chloride and the corresponding bromides.
- B-stage or thermoplastic hexasubstituted polymelamines are obtained. These B-stage polymelamines can also be stored for prolonged periods of time, without curing, yet remain usable at any subsequent time and are readily cured by the application of heat.
- the claimed poly(hexasubstituted melamines) are particularly well suited for use in corrosive atmospheres and in environments subject to high temperatures because of their solvent resistance and high thermal stability and the fact that no volatile material is given off during polymerization. They may be modified with a variety of fibrous and finely divided inert filler materials such as clay, quartz flour, asbestos, glass filaments and woven and unwoven fabrics, ceramic particles and fibers, metal particles and fibers and carbon powders and fibers.
- Laminates and composites are readily made by impregnating the filler material with a mixture of alkylene bis(N-substituted cyanamides) or a mixture ofalkylene bis-(N-substituted cyanamides) and an effective amount of the selected Lewis acid catalyst and simply heating the mixture to cause polymerization. If it is desired to produce storable and subse quently processible (i.e. moldable) laminates or molded composites. the heating may be carried out only to the formation of B-stage polymer. At a later time such green" laminates or composites can be shaped to desired form and cured in that condition.
- Laminates and composites with filler materials may also be made using B-stage oligomers that have been EXAMPLE 1
- a mixture of parts of hexamethylene bis-N- methylcyanamide and two parts of iridium trichloride is sealed in a Carius tube and heated at 200 C. for 20 hours.
- the tube is cooled, then opened to yield a brittle, glassy, amber B-stage polymer having a glass transition temperature (T,,) of 65 to 87 C.
- the B-stage polymer is cured to a tough, thermoset polymer by heating at about 200 C. for 14 hours.
- Example 2 The procedure described in Example l is carried out using tetramethylene bis-N-ethylcyanamide. A poly(- hexasubstituted melamine) similar to that obtained in Example 1 is obtained.
- EXAMPLE 3 A mixture of two parts of trimethylene bis-N- ethylcyanamide and O.l part of indium trichloride was heated in a test tube at 200 C. for 24 hours. A poly(- hexasubstituted melamine) similar to that obtained in Example I was obtained on cooling.
- Example 4 The procedure described in Example 2 is carried out using l,3-bis-[4-(N-cyanopiperidyl)] propane, which has the structure and which is prepared by cyanation of commercially available 1,3-di-(4-piperidyl) propane by known methods.
- a poly(hexasubstituted melamine) B-stage polymer similar to that obtained in Example 1 is obtained on cooling. When heated for 24 hours at 200 C. this material cures to a hard, tough solid which is insoluble in all common solvents.
- EXAMPLE 5 A mixture of 30 parts l,3-bis-[4-cyanopiperidyl)] propane and l .2 parts of indium trichloride is heated at C. with stirring for six hours to form a B-stage poly(hexasubstituted melamine). On cooling, a lowmelting waxlike solid is obtained, which has average molecular weight of about 510.
- EXAMPLE 6 'Thirty parts of the B-stage hexasubstituted melamine polymer prepared in Example 5 is diluted with about 15 parts of chloroform and used to saturate a glass cloth. The cloth is air dried, cut into portions and a lO-ply laminate assembled in a mold. The mold is placed in a press and heated at 225 C.
- R and R are each lower alkyl, cyclo-lower alkyl, aryl, and alkaryl, each being optionally substituted by one or two chlorine or one to three fluorine atoms or by lower perfluoroalkyl, lower alkoxy or aralkoxy group;
- R, R and R are the same or difi'erent and are divalent alkylene having from 1 to carbon atoms, cycloalkylene having from 3 to 6 carbon atoms, piperidyl and R, R and R taken together with the two triazine nitrogen atoms to which they are attached form a divalent l,3-bis[4-l-piperidyl)] trimethylene radical.
- B-stage polymer according to claim 1 in ther moplastic, chlorinated hydrocarbon-soluble form, being capable of further curing to thermoset condition upon further heating thereof.
- Polymer according to claim 1 consisting essentially of repeating units having the formula wherein n is an integer from 2 to 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Poly(hexasubstituted melamines) prepared by the Lewis acid catalyzed polymerization of alkylene bis-(N-substituted cyanamides) of the formula
wherein R1 and R2 are broadly alkyl or aryl and R3 is alkylene, such polymers being curable to a storable B-stage as well as fully cured condition, having excellent high temperature stability and being useful as structural adhesives or binders.
wherein R1 and R2 are broadly alkyl or aryl and R3 is alkylene, such polymers being curable to a storable B-stage as well as fully cured condition, having excellent high temperature stability and being useful as structural adhesives or binders.
Description
United St Langager 1 1 POLYlHEXASUBSTITU'l'ED MELAMINES) [75] Inventor: Bruce A. Langager. St. Anthony Village. Minn.
1731 Assignee: Minnesota Mining and Manufacturing Company. St. Paul. Minn.
[22] Filed: June 6. 1974 [21] App1.N0.:476.9l1
Related US. Patent Documents Reissue of:
[64] Patent No.: 3,779,997
Issued: Dec. 18, 1973 Appl. No.: 261,924 Filed: June 12. 1972 [52] US. Cl 260/77.5 R; 161/190; 260/2 R; 260/37 N 1511 Int. Cl C08g 33/02 {581 Field 0! Search 260/77.5 R. 2 R. 551 C. 260/249.6
[56] References Cited UNITED STATES PATENTS 3.130.224 4/1964 Sugino 260/55 R 3.155.628 11/1964 Bloomfield 260/2 R 3.170.895 2/1965 Rcimschuesscl ct a1. 260/2 R E Re. 28,495
Reissued July 29, 1975 3.775.380 11/1973 Miller 260/2 R FOREIGN PATENTS OR APPLICATIONS 253.352 1967 U S S.R 7.60/2 R 1.009.892 1965 United Kingdomum. 260/2 R 1.164.523 9/1969 United Kingdom. 260/2 R 1.309.517 1962 France l r 260/2 R 1.523.551 5/1968 France r. 260/2 R Primary Examiner-H. S. Cockeram Attorney, Agent, or FirmAlexander. Sell. Steldt & DeLaHunt [57] ABSTRACT Poly(hexasubstituted melamines) prepared by the Lewis acid catalyzed polymerization of alkylene bis- (N-substituted cyanamides) of the formula wherein R and R are broadly alkyl or aryl and R is alkylene. such polymers being curable to a storable B-stage as well as fully cured condition. having excellent high temperature stability and being useful as structural adhesives or binders.
13' Claims, No Drawings POLY(HEXASUBSTITUTED MELAMINES) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This invention relates to high temperature stable polymers, and more particularly to high temperature stable polymers prepared from alkylene bis-(N- substituted cyanamides). The polymers of this invention contain melamine (triamino-s-triazine) segments in which each of the amine hydrogens has been replaced by an organic group, and these segments are linked by alkylene groups.
BACKGROUND OF THE INVENTION Polymers containing melamine segments have been prepared before. For example, in US. Pat. No. 2.824.088 there are described polymers containing triarylamino-s-triazine residues which are prepared by the reaction of trihalo-s-triazines with diamines, the reaction taking place with the liberation of hydrogen halide. The polymers retain a hydrogen atom on each of the amine groups present on each of the triazine segments, hence the polymer has a limited thermal stability.
Polymers containing melamine segments in which all of the hydrogens of each of the amine groups present on each of the triazine segments of the polymer have been replaced by an organic group are described in US. Pat. Nos. 3,382,221 and 3,277,065. These polymers, however, are prepared by the free radical catalyzed polymerization of hexasubstituted melamines wherein at least four of the substituents are allyl groups, and polymerization takes place via addition reaction at the allylic double bond. Moreover, polymers described in these patents must be prepared in an inert atmosphere because the presence of oxygen in more than trace amounts inhibits the polymerization.
Polymers containing melamine segments have also been prepared by polymerization of organic biscyanamides. For example. in U.S. Pat. No. 3.291.673 and British Pat. No. l.009.892 it is disclosed that alkylenedicyanamides may be polymerized by keeping them, with or without a basic accelerator, in a liquid state at an appropriate temperature. The polymers obtained, however, although polymerized without the elimination of volatile by-products, contain hydrogen atoms attached to the nitrogen atoms. in addition, US. Pat. No. 3.303.101 describes the preparation of copolymers by heating a mixture of monocyanamides and dicyanamides. According to the disclosure of Smolin and Rapoport, "The Chemistry of Heterocyclic Compounds." lnterscience. New York. 1959.2 page 357. the polymers described in these patents most likely contain iso-melamine segments.
Other previously described polymers containing melamine, or perhaps iso-melamine, segments are described in German Pat. Nos. 1.958.320 and 1.965.907 and Netherlands Pat. No. (J/05.451. which describe polymeric products that are obtained by the reaction of organic poly (N-substituted cyanamides) and hydroxy or thiol compounds or mixtures thereof. These polymers. however. are believed to be significantly less stable than the polymers according to the present invention.
SUMMARY OF THE INVENTION The present invention provides novel thermosetting poly(hexasubstituted melamines) that are readily prepared by the Lewis acid catalyzed polymerization of correspondingly substituted bis (Nsubstituted cyanamides), a process that does not require condensation with elimination of volatile by-products, does not require an inert atmosphere, does not involve the use of electronegative group-activated compounds, nor the use of free radical-generating catalysts or copolymerization with compounds containing active hydrogen, hydroxyl or thiol groups. Moreover, such poly(hexasubstituted melamines) possess good high temperature stability.
It is, accordingly, an object of the present invention to provide poly(hexasubstituted melamines) having useful high temperature stability and excellent dielectric properties.
It is also an object of the present invention to provide a process for the production of poly(hexasubstituted melamines) that does not require condensation with elimination of undesirable volatile by-products.
It is also an object of the present invention to provide a process for the production of poly(hexasubstituted melamines) by Lewis acid catalyzed polymerization of divalent bis-(N-substituted cyanamides).
It is a further object of the present invention to provide a process for the production of poly(hexasubstituted melamines) that does not involve use of elec tro-negative group-activated compounds, free radical generating catalysts, or copolymerization with compounds containing active hydrogen or thiol groups.
These and other objects and advantages of the present invention will be readily apparent to one skilled in the art upon reading the more detailed description that follows.
As used throughout this specification and the claims, the terms "lower alkyl and lower alkoxy" embrace both straight and branched chain alkyl and alkoxy radicals. respectively. containing from I to 6 carbon atoms. for example, but without limitation thereto, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl. sec-pentyl. n-hexyl. 2-ethylbutyl. 2.3- dimethylbutyl and the like in the case of1ower alkyl," and methoxy, ethoxy, n-propoxy, isopropoxy, nbutoxy, sec-butoxy, tert-butoxy, n-pentoxy, secpentoxy, n-hexyloxy. 2-ethylbutoxy. 2.3-dimethylbutoxy and the like in the case of lower alkoxy"; the term cyclo-lower alkyl embraces lower alkyl-substituted and unsubstituted cycloalkyl radicals containing a total of from 3 to 9 carbon atoms. including, when substituted. the carbon atoms in the lower alkyl substituent or substituents, for example, but without limitation thereto, cyclopropyl, cyclobutyl, methylcyclopropyl, cyclopentyl. ethylcyclopropyl. dimethylcyclopropyl. Z-methylcyclobutyl. 3-ethylcyclopropyl. 2.3-dimethylcyclobutyl. 2-ethylcyclobutyl. 3- ethylcyclobutyl. cycloheptyl. 2.3-diethylcyclopropyl. 2-methyl-3-ethylcyclopropyl. 2.3.4-trimethylcyclobu tyl. 2-ethyl-3-methylcyclohexyl. cycloheptyl. cyclononyl and the like; the term aryl" embraces both substituted and unsubstituted monovalent organic radicals derived from aromatic hydrocarbons by the removal of one hydrogen atom, for example, but without limitation 3 thereto. phenyl. naphthyl. anthryl. pyridyl. carbazyl. indolyl. Z-triazinyl. furyl. benzoxazolyl. benzthiazolyl and the like. such radicals. if desired. optionally bearing one or more lower alkyl. lower alkoxy. aryl. halogen. carbo-lower alkoxy. arylsulfonyl or nitro substituents'. the term aryloxy" embraces substituted or unsubstituted aryloxy radicals. for example. but without limitation thereto. phenoxy. Imaphthyloxy. 2- naphthyloxy. lanthryloxy.Z-anthryloxy.9-anthryloxy and the like. such radicals. if desired, optionally bearing one or more lower alkyl, lower alkoxy. aryl. halogen, carbo-lower alkoxy. arylsulfonyl or nitro substituents; the term alkylene embraces both straight and branched chain alkylene radicals of the formula C I-[ wherein n is an integer of from I to and the term halogen" includes chloro and fluoro.
The poly(hexasubstituted melamines) of the present invention consist essentially of segments (repeating units) having the structural formula together with the two nitrogen atoms to which they are attached form a divalent radical of the formula In the B" stage. the materials are oligomeric and thermoplastic. They apparently contain a mixture of trimeric to hexameric chains of starting dicyanamides. which do not have more than about two triazine rings in any one polymer chain. Their average molecular weight in the B stage is from about 300 to 3.000. At this stage they retain useful solubility in chlorinated hydrocarbon such as methylene chloride. chloroform and the like.
In carrying out the process aspect of the present invention the poly( hexasubstituted melamine) final product is prepared by heating. in the presence of a Lewis acid catalyst. an alkylene bis(N'substituted) cyanamide of the formula wherein R. R and R are as defined hereinabove. or a mixture of such bis-cyanamides in which R" is one or more different divalent radicals. i.e. is R or R v Among the alkylene bis-(Nsubstituted cyanamides) that may be used to prepare the poly(hexasubstituted melamines) according to the present invention are bis- (N-alkylcyanamides). such as. for example. ethylene bislN-methylcyanamide). propylene bis-(N- ethylcyanamide). hexamethylene bis-(N butylcyanamide) and dodecylene bis-( N- butylcyanamide); alkylene bis-(N- cycloalkylcyanamides), such as. for example. propylene bis-(N-cyclohexycyanamide); alkylene bis-(N- arylcyanamides). such as. for example. propylene bis- (N-phenylcyanamide) and propylene bis-(N- benzylcyanamide); alkylene bis-cyanamides with mixed nitrogen substituents, such as, for example. ethylene bis-(N-methyl-N'-phenyl bis-cyanamide); and alkylene bis-[N-(substituted aryl) cyanamides]. such as. for example, ethylene bis-[N-(4-chlorophenyl) cyanamide], butylene bis-[N-(methoxy phenyl) cyanamide] and butylene bis[l\l(4-phenoxyphenyl) cyanamide].
The alkylene bis-(N-substituted cyanamide) starting materials are prepared by known'procedures described in the literature. including. for example, the dehydration of bis-ureas as described by Robinson. Can. J. Chem. 32. 32, 901 (1954); the dehydration of thioureas as described by Kurzer. J. Chem. Soc. l950, 3269 and the preparation of l.4-dicyanopiperazine as described by Kramer. Chem. Zentral. l9l0 l. 1532 and Franchimont and Kramer, Rec. trav. chem. 3l. 64 (1912).
The poly(hexasubstituted melamines) of the present invention are prepared by heating one or more alkylene bis-(N-substituted cyanamides) with a Lewis acid catalyst. The temperature and time of heating are varied according to the amount of and nature of the Lewis acid catalyst chosen to effect the polymerization. Generally. temperatures range from about to 350 C. and polymerization times from about one hour to about 48 hours. and from about 0.5 to about 15 weight percent of Lewis acid catalyst is used. The higher the tempera ture and the greater the amount of catalyst used. the less is the time required to reach the B-stage and the thermoset stage of the polymer. The preferred conditions for preparing the poly(hexasubstituted melamines) are to heat the alkylene bis-(N-substituted cyanamides) at a temperature from 200 to 250 C. for from about two to 24 hours in the presence of l to 5 weight percent of a Lewis acid catalyst.
The polymerization reaction is readily controlled. For any given amount of catalyst. the polymerization proceeds with controlled application of heat to the B- stage. where the polymers formed are soluble and thermoplastic. or is carried on to the thermoset stage. where the polymers are crosslinked and therefore insoluble. By discontinuing heating at the B-stage. regardless of whether a high or low percentage of catalyst is employed in the polymerization. the polymerization can be halted. At this stage the polymer may be stored at lower temperature for an essentially unlimited period of time and. when desired. converted to the thermoset stage simply by the application of heat.
Lewis acid that may be used as catalyst for the polymerization of the alkylene bisJN-substituted cyanamides) is defined as a substance that is electron deficient and tends to form a coordinated bond by accepting a pair of electrons. Suitable Lewis acids are selected from the hard and intermediate Lewis acids as classified by Pearson, J. Am. Chem. Soc. 85, 3633 (i963) and include but are not limited to aluminum chloride, aluminum bromide, aluminum iodide, stannic chloride, antimony trichloride, indium trichloride, cobaltic chloride, cobaltic bromide, indium oxide, cobaltic oxide, ferric oxide, ferric chloride, manganic acetate, manganic acetylacetonate, manganous acetylacetonate, titanium tetrachloride, titanium dioxide, boron trifluoride, boron trifluoride etherate, boron trichloride, ferrous chloride, cobaltus chloride, nickel chloride, manganese, dioxide, zinc chloride, lead chloride, lead iodide and the like. Some of these materials are of low activity and are essentially fillers. When used they may require the addition of more active catalyst to achieve complete cure within a practical length of time.
The preferred Lewis acid catalysts are those that have a low volatility, such as, for example, Lewis acids that do not volatilize or decompose below about 200 C., and particularly indium trichloride or zinc chloride and the like.
The polymerization of the alkylene organic bis-(N- substituted cyanamides) according to the present invention may be carried out in the presence of volatile Lewis acid catalysts; however, with such catalysts it is necessary that pressure equipment be utilized during the polymerization to confine the catalyst. The preferred catalysts are indium trichloride, stannic chloride, antimony trichloride, cobaltic chloride, zinc chloride, ferric chloride and the corresponding bromides.
By performing the polymerization of the alkylene bis- (N-substituted cyanamides) at lower polymerization temperatures and for shorter polymerizing periods, as described above, B-stage or thermoplastic hexasubstituted polymelamines are obtained. These B-stage polymelamines can also be stored for prolonged periods of time, without curing, yet remain usable at any subsequent time and are readily cured by the application of heat.
The claimed poly(hexasubstituted melamines) are particularly well suited for use in corrosive atmospheres and in environments subject to high temperatures because of their solvent resistance and high thermal stability and the fact that no volatile material is given off during polymerization. They may be modified with a variety of fibrous and finely divided inert filler materials such as clay, quartz flour, asbestos, glass filaments and woven and unwoven fabrics, ceramic particles and fibers, metal particles and fibers and carbon powders and fibers.
Laminates and composites, for example, are readily made by impregnating the filler material with a mixture of alkylene bis(N-substituted cyanamides) or a mixture ofalkylene bis-(N-substituted cyanamides) and an effective amount of the selected Lewis acid catalyst and simply heating the mixture to cause polymerization. If it is desired to produce storable and subse quently processible (i.e. moldable) laminates or molded composites. the heating may be carried out only to the formation of B-stage polymer. At a later time such green" laminates or composites can be shaped to desired form and cured in that condition.
Laminates and composites with filler materials may also be made using B-stage oligomers that have been EXAMPLE 1 A mixture of parts of hexamethylene bis-N- methylcyanamide and two parts of iridium trichloride is sealed in a Carius tube and heated at 200 C. for 20 hours. The tube is cooled, then opened to yield a brittle, glassy, amber B-stage polymer having a glass transition temperature (T,,) of 65 to 87 C.
The B-stage polymer is cured to a tough, thermoset polymer by heating at about 200 C. for 14 hours.
EXAMPLE 2 The procedure described in Example l is carried out using tetramethylene bis-N-ethylcyanamide. A poly(- hexasubstituted melamine) similar to that obtained in Example 1 is obtained.
EXAMPLE 3 A mixture of two parts of trimethylene bis-N- ethylcyanamide and O.l part of indium trichloride was heated in a test tube at 200 C. for 24 hours. A poly(- hexasubstituted melamine) similar to that obtained in Example I was obtained on cooling.
EXAMPLE 4 The procedure described in Example 2 is carried out using l,3-bis-[4-(N-cyanopiperidyl)] propane, which has the structure and which is prepared by cyanation of commercially available 1,3-di-(4-piperidyl) propane by known methods. A poly(hexasubstituted melamine) B-stage polymer similar to that obtained in Example 1 is obtained on cooling. When heated for 24 hours at 200 C. this material cures to a hard, tough solid which is insoluble in all common solvents.
EXAMPLE 5 A mixture of 30 parts l,3-bis-[4-cyanopiperidyl)] propane and l .2 parts of indium trichloride is heated at C. with stirring for six hours to form a B-stage poly(hexasubstituted melamine). On cooling, a lowmelting waxlike solid is obtained, which has average molecular weight of about 510.
EXAMPLE 6 'Thirty parts of the B-stage hexasubstituted melamine polymer prepared in Example 5 is diluted with about 15 parts of chloroform and used to saturate a glass cloth. The cloth is air dried, cut into portions and a lO-ply laminate assembled in a mold. The mold is placed in a press and heated at 225 C. for one hour with contact wherein R and R are each lower alkyl, cyclo-lower alkyl, aryl, and alkaryl, each being optionally substituted by one or two chlorine or one to three fluorine atoms or by lower perfluoroalkyl, lower alkoxy or aralkoxy group; R, R and R are the same or difi'erent and are divalent alkylene having from 1 to carbon atoms, cycloalkylene having from 3 to 6 carbon atoms, piperidyl and R, R and R taken together with the two triazine nitrogen atoms to which they are attached form a divalent l,3-bis[4-l-piperidyl)] trimethylene radical.
2. Polymer according to claim 1 in thermoset, insoluble, cured form.
3. B-stage polymer according to claim 1, in ther moplastic, chlorinated hydrocarbon-soluble form, being capable of further curing to thermoset condition upon further heating thereof.
4. Polymer according to claim 4, wherein R" is hexamethylene, tetramethylene or trimethylene.
5. Polymer according to claim 4, wherein R is methyl or ethyl.
6. Polymer according to claim 1, wherein R. R and R taken with the two nitrogen atoms to which they are attached, form a divalent l,3-bis-[4-( l-piperidyl)] trimethylene radical.
7. B"-stage polymer according to claim 3, in which R is methyl or ethyl and R" is hexamethylene, tetramethylene or trimethylene.
8. Polymer according to claim 1, consisting essentially of repeating units having the formula wherein n is an integer from 2 to 6.
9. Polymer according to claim 8. wherein n is 3. l0. Polymer according to claim 8. wherein n is 6. ll. Polymer according to claim 1. consisting essentially of repeating units having the formula 12. Process for making polymers according to claim 1, which comprises heating, in the presence of a Lewis acid catalyst, a compound of the formula N n C-N s (C z).-| s N-- N N 1 ll d-ND-KIHI). s N-c N N \z c [14. Poly-(hoxasubstituted melamine) consisting of segments having the formula wherein R and R are each lower alkyl. cycle-lower alkyl, aryl and alkaryl, each being optionally substituted by one or two chlorine or I to 3 fluorine atoms or by 5 lower perfluoroalkyl. lower alkoxy or arallcoxy group] llll
Claims (13)
1. POLY(HEXASUBSTITUTED MELAMINES) CONSISTING OF SEGMENTS HAVING THE FORMULA
2. Polymer according to claim 1 in thermoset, insoluble, cured form.
3. ''''B''''-stage polymer according to claim 1, in thermoplastic, chlorinated hydrocarbon-soluble form, being capable of further curing to thermoset condition upon further heating thereof.
4. Polymer according to claim 4, wherein R3 is hexamethylene, tetramethylene or trimethylene.
5. Polymer according to claim 4, wherein R2 is methyl or ethyl.
6. Polymer according to claim 1, wherein R1, R2 and R3, taken with the two nitrogen atoms to which they are attached, form a divalent 1,3-bis-(4-(1-piperidyl)) trimethylene radical.
7. ''''B''''-stage polymer according to claim 3, in which R2 is methyl or ethyl and R3 is hexamethylene, tetramethylene or trimethylene.
8. Polymer according to claim 1, consisting essentially of repeating units having the formula
9. Polymer according to claim 8, wherein n is 3.
10. Polymer according to claim 8, wherein n is 6.
11. Polymer according to claim 1, consisting essentially of repeating units having the formula
12. Process for making polymers according to claim 1, which comprises heating, in the presence of a Lewis acid catalyst, a compound of the formula
13. A poly(hexasubstituted melamine) consisting essentially of repeating units having the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47691174 USRE28495E (en) | 1972-06-12 | 1974-06-06 | Poly(hexasubstituted melamines) |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26192472A | 1972-06-12 | 1972-06-12 | |
| US47691174 USRE28495E (en) | 1972-06-12 | 1974-06-06 | Poly(hexasubstituted melamines) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE28495E true USRE28495E (en) | 1975-07-29 |
Family
ID=26948921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US47691174 Expired USRE28495E (en) | 1972-06-12 | 1974-06-06 | Poly(hexasubstituted melamines) |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE28495E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352762A (en) * | 1990-03-30 | 1994-10-04 | Hitachi, Ltd. | Multilayer printed circuit board and production thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU253352A1 (en) * | Московский химико технологический институт И. еева | METHOD OF OBTAINING THERMAL-RESISTANT POLYMERS | ||
| FR1309517A (en) * | 1961-11-18 | 1962-11-16 | Nippon Carbide Kogyo Kk | New polymers, their preparation process and their application as adhesive and film-forming material |
| US3130224A (en) * | 1961-10-26 | 1964-04-21 | Nippon Carbide Kogyo Kk | Manufacturing method of alkylenedicyanamide |
| US3155628A (en) * | 1960-03-22 | 1964-11-03 | Artrite Resins Ltd | Production of polymers containing s-triazine nuclei linked together by a nitrogen atom comprising reacting s-triazines with nitrogen compounds |
| US3170895A (en) * | 1962-08-23 | 1965-02-23 | Herbert K Reimschuessel | Triazine polymers and method of making same |
| GB1009892A (en) * | 1961-10-31 | 1965-11-17 | Nippon Carbide Kogyo Kk | Alkylenedicyanamide polymers |
| FR1523551A (en) * | 1966-04-23 | 1968-05-03 | Bayer Ag | Process for the preparation of polymer products derived from cyanamides |
| GB1164523A (en) * | 1966-04-23 | 1969-09-17 | Bayer Ag | Polymers and Production thereof |
| US3775380A (en) * | 1971-09-01 | 1973-11-27 | Texaco Inc | Polymerization of aromatic nitriles |
-
1974
- 1974-06-06 US US47691174 patent/USRE28495E/en not_active Expired
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU253352A1 (en) * | Московский химико технологический институт И. еева | METHOD OF OBTAINING THERMAL-RESISTANT POLYMERS | ||
| US3155628A (en) * | 1960-03-22 | 1964-11-03 | Artrite Resins Ltd | Production of polymers containing s-triazine nuclei linked together by a nitrogen atom comprising reacting s-triazines with nitrogen compounds |
| US3130224A (en) * | 1961-10-26 | 1964-04-21 | Nippon Carbide Kogyo Kk | Manufacturing method of alkylenedicyanamide |
| GB1009892A (en) * | 1961-10-31 | 1965-11-17 | Nippon Carbide Kogyo Kk | Alkylenedicyanamide polymers |
| FR1309517A (en) * | 1961-11-18 | 1962-11-16 | Nippon Carbide Kogyo Kk | New polymers, their preparation process and their application as adhesive and film-forming material |
| US3170895A (en) * | 1962-08-23 | 1965-02-23 | Herbert K Reimschuessel | Triazine polymers and method of making same |
| FR1523551A (en) * | 1966-04-23 | 1968-05-03 | Bayer Ag | Process for the preparation of polymer products derived from cyanamides |
| GB1164523A (en) * | 1966-04-23 | 1969-09-17 | Bayer Ag | Polymers and Production thereof |
| US3775380A (en) * | 1971-09-01 | 1973-11-27 | Texaco Inc | Polymerization of aromatic nitriles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352762A (en) * | 1990-03-30 | 1994-10-04 | Hitachi, Ltd. | Multilayer printed circuit board and production thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5003039A (en) | Amino phenyl containing curing agent for high performance phthalonitrile resin | |
| CA1319214C (en) | Blended polyamide oligomers | |
| CA1336098C (en) | Heterocycle sulfone oligomers and blends | |
| JP2925229B2 (en) | Sintered polybenzimidazole / polyarylene ketone products and manufacturing method | |
| EP0309649A2 (en) | High performance heterocycle oligomers and blends | |
| US4876328A (en) | Polyamide composition | |
| JPS63297361A (en) | Imidophenylamine and manufacture | |
| US3909489A (en) | Polyesters and copolyesters having improved flame retardancy | |
| USRE28495E (en) | Poly(hexasubstituted melamines) | |
| US3779997A (en) | Poly(hexasubstituted melamines) | |
| US3817920A (en) | Thermosetting poly(hexasubstituted melamines) | |
| JP2962515B2 (en) | Polybenzimidazole / polyarylene ketone molded article and production method | |
| EP0407176B1 (en) | Process for producing a cured cyanate ester resin product | |
| US6583255B1 (en) | Polyester oligomer | |
| US3853819A (en) | Flame resistant thermoplastic polyesters | |
| US3694408A (en) | Organic nitrogenous compounds and polymers thereof | |
| US3554971A (en) | Amorphous or weakly crystalline aromatic polyamides | |
| EP0510818B1 (en) | Blends of polybenzimidazoles and aromatic polyamides, aromatic polyamide-hydrazides or aromatic polyamides containing heterocyclic linkages | |
| CN107400235B (en) | Cyanate hybrid polymers and cyanate composites | |
| US3244647A (en) | Preparation of polyphosphonamides | |
| US3719640A (en) | Poly(amide-imide)polymers having recurring diketopiperazine groups | |
| US3578644A (en) | Hydroxyl modified polybenzimidazoles | |
| Stille et al. | The Cross-Linking of Thermally Stable Aromatic Polymers by Aryl Cyanate Cyclotrimerization | |
| KR20220151567A (en) | Branched poly(lactic acid-3-hydroxypropionic acid) polymer and method for preparation thereof | |
| Augl et al. | Thermomechanical behavior of a polyphenylquinoxaline |