AU2003250494A2 - Inclusion complexes of cyclic macromolecular organic compounds and polymerization thereof - Google Patents
Inclusion complexes of cyclic macromolecular organic compounds and polymerization thereof Download PDFInfo
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- AU2003250494A2 AU2003250494A2 AU2003250494A AU2003250494A AU2003250494A2 AU 2003250494 A2 AU2003250494 A2 AU 2003250494A2 AU 2003250494 A AU2003250494 A AU 2003250494A AU 2003250494 A AU2003250494 A AU 2003250494A AU 2003250494 A2 AU2003250494 A2 AU 2003250494A2
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- Australia
- Prior art keywords
- complex
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- organic solvent
- homopolymers
- polymerization
- Prior art date
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Links
- 125000004122 cyclic group Chemical group 0.000 title claims description 14
- 150000002894 organic compounds Chemical class 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 title description 25
- 238000000034 method Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229920001519 homopolymer Polymers 0.000 claims description 26
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- -1 cyclic organic compound Chemical class 0.000 claims description 9
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 claims description 9
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
- 150000001923 cyclic compounds Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 8
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 5
- 150000003983 crown ethers Chemical class 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 claims description 4
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002739 cryptand Substances 0.000 claims description 4
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 claims description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 49
- 229920000858 Cyclodextrin Polymers 0.000 description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- 229940097362 cyclodextrins Drugs 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- ZENYUPUKNXGVDY-UHFFFAOYSA-N 1,4-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=C(C(C)=C)C=C1 ZENYUPUKNXGVDY-UHFFFAOYSA-N 0.000 description 1
- UKQBWWAPJNHIQR-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(CO)(CO)CO UKQBWWAPJNHIQR-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZZASRJYLQUPYFI-UHFFFAOYSA-N chloroform;n,n-dimethylformamide Chemical compound ClC(Cl)Cl.CN(C)C=O ZZASRJYLQUPYFI-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- ORPJQSFBLBHKPN-UHFFFAOYSA-N dichloromethane;methylsulfinylmethane Chemical compound ClCCl.CS(C)=O ORPJQSFBLBHKPN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002174 soft lithography Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
WO 2005/014671 PCT/IB2003/003593 INCLUSION COMPLEXES OF CYCLIC MACROMOLECULAR ORGANIC COMPOUNDS AND POLYMERIZATION THEREOF Technical Field The present invention relates to an inclusion complex containing monomers with multiple unsaturated and cyclic compound s represented by the general formula Ax By, wherein the monomer containing X units of vinyl unsaturation and B is a cyclic host compound with Y units, and also, a process for the preparation of soluble homo-polymers with unsaturation group from the inclusion complex.
Background Art Traditionally polymers have been classified into two categories viz thermoplastics and thermosets depending upon their melting and solubility behavior. The thermoplastics on heating, are converted to a molten state and on cooling return to solid state; reversibly.
This property is made use of in shaping the polymers in various forms such as films, sheets, rods and other molded products. Also these polymers are soluble in solvents and can be converted into films by solution casting and solvent evaporation. In contrast, the thermoset products cannot be converted into a molten state or dissolved in solvents.
Although these materials offer enhanced mechanical and thermal properties over the thermoplastics, they cannot be readily processed into finished products using processing techniques, commonly used in the case of thermoplastics. Similarly the properties of the thermoplastics cannot be significantly enhanced after converting the resins into finished products since there is no scope to modify the polymer structure chemically after the polymerization is completed.
In few cases such as the phenolics, ureas and melamines, a two stage process is adopted whereby polymerization is first limited to a stage where the polymer can be fused into a molten state or dissolved in a solvent and then cross linked further into an infusible, insoluble product which has enhanced mechanical and thermal properties.
Thermosetting polymers containing reactive groups are used as coatings. These polymers are usually in the form of lattices that are further crosslinked either thermally or by addition of functional groups like isocyanates, amines or metal ions. By formation of a network these resins attain their desired properties insolubility in most organic solvents, good water resistance and hardness (Van E.S.JJ in Polymeric Dispersions Principles and Applications. Asua, J. M Kluwer Publishers, 1997, p. 451; Ooka, M., WO 2005/014671 PCT/IB2003/003593 2 Ozawa, H. Progress in Organic Coatings. vol 23, 1994, p.325 Photosensitive groups like cinnamoyl or azo type do not undergo thermal free radical polymerization but can be polymerized by UV irradiation. Polymers containing these functional groups can be cured by exposure to UV irradiation (Mueller, Mueller, Nuyken, O. Makromolecular.
Chem. Rapid. Communications., 13, 289, 1992; Raanby, B in Current Trends in Polymer Photochemistry. Norman, Allen London, UK, 1995, p.23). These materials can be used for non linear optics.
In the case of unsaturated polyester resins, a polyester resin containing unsaturated sites is prepared by condensation polymerization using maleic anhydride and or fumaric acid as the acid component. The resin, diluted with other vinyl monomers such as styrene, methyl methacrylate, allyl acrylate etc is cast into the desired form and then polymerized further to a crosslinked product in the presence of free radical initiators and accelerators activators. While these resins are routinely used in the electrical and automobile industry, their scope is restricted. A large number of monomers such as styrene, methyl methacrylate, acrylonitrile, vinyl acetate, hydroxyethyl methacrylate, acrylamide and so on when polymerized by conventional methods of free radical polymerization result in solvent soluble melt fusible resins which can be then converted to desired products.
But as mentioned earlier, these products cannot be subsequently transformed into insoluble, infusible products, since there are no potential polymerizable sites present in the structure. On the other hand polymerization of these monomers with monomers containing multiple unsaturated sites viz ethylene glycol dimethacrylate, divinyl benzene, allyl acrylate, vinyl methacrylate results in the formation of three dimensional crosslinked products which cannot be further converted into useful forms since they are neither soluble in solvents nor are they converted into a molten state on the application of heat.
The need for polymers which are solvent soluble and thermally fusible and which could be later converted into products having enhanced mechanical thermal solvent resistance properties is increasing with growing applications of polymers in the field of electronics, photoresists, controlled release delivery systems, micro electro mechanical systems (MEMS) etc.
Injectable polymer based ceramics are being increasingly investigated for fabrication of high temperature MEMS. (Liew, Zhang, W.L: Bright, Linan, Dunn, M.L.
Raj, Sensors and Actuators A 89, 64, 2001) Polymeric precursors are converted to high performance ceramic microstructures using soft lithography (Yang, H; Deschatelects, WO 2005/014671 PCT/IB2003/003593 3 Brittain, S.T. and Whitesides, Advanced Materials, 13,54 2001). It therefore follows that there is a need to develop methodologies, which will help manipulate properties of polymers for applications in MEMS devices.
In the microstereolithography process, three dimensional microstructures are constructed by solidifying the liquid monomers e.g. Zhang et al fabricated micro gears using microstereolithography (Zhang, X; Juang, XN,, Sun, C. Sensors Actuators, A, 77, 149, 1999). In micro fluidic devices, polymers offer versatility and ease of processing over glass Saper, Ford, Qi, S. McCarley, Kelly, K. and Murphy, Analytical Chemistry, 72, 643 A, 2000).
In the field of controlled release delivery system a drug coated from a polymer solution or a dispersion to provide a coating can then be cross linked as to present a barrier for the permeation of the drug from the coated layer and thus manipulate the rate of release of the drug from the device.
Nanoparticles constitute an important building block for materials to be used in medical, mechanical and electronic applications (Xia, Gates, Yin, Lu, Advanced Materials, 12, 693, 2000). Meccrreyes et al synthesized nanoparticles by self cross linking of polymers in dilute solutions. In this approach, acrylate methacrylate pendant groups were created on polymer backbone and subsequently polymerized to generate self cross linked polymer particles (Meccereyes, Lee, V, Hawker, Hedrick, Wursch, A; Volksen, V; Magbitang, T; Huang, Miller, Advanced Materials, 13, 204, 2001)..
In yet another approach, Wooley (Wooley, JPolym. Sci. A, Polymer Chemistry, 38, 1397 2000), prepared shell crosslinked knedels by organizing the polymers into micellar assemblies and then bringing about intramicellar crosslinking. Clearly, polymers which can be solubilized and contain unsaturated sites which can be subsequently polymerized, is an important class of materials which has a wide range of applications.
Free radical polymerization of monomers comprising multiple unsaturated groups leads to insoluble polymers. There are few reports on the controlled polymerization of monomers containing multiple unsaturated groups using anionic polymerization. Thus anionic polymerization of 1,4 divinyl or 1,4-diisopropenylbenzene gave reactive microgels containing high amount of pendant vinyl groups. But this method is restricted to divinyl compounds, which are amenable to anionic polymerization (Hiller, J. Funke, W.
Angew. Makromolecular. Chemistry., 76/77, 161, 1979. Wolfgang, S. Funke, W.
WO 2005/014671 PCT/IB2003/003593 Makromolecular. Chemistry., 179, 2145, 1978. and requires monomers of extremely high purity and very low temperature Recently Guan (2002) reported the synthesis of hyper branched polymers by cobalt mediated free radical polymerization of ethylene glycol dimethacrylate (Guan, Z. Journal ofAmerican Chemical Society. 124, 5616, 2002) which resulted in a soluble polyethylene glycol dimethacrylate polymer containing unsaturation However, this method is specific to ethylene glycol dimethacrylate and cannot be readily extended to other monomers containing multiple unsaturated sites A wider range of cyclic compounds such as cyclodextrins, calixarenes, cryptands, and crown ethers are known to form host guest complexes and have been widely exploited commercially e.g. a number of drugs which are poorly water soluble and hence are poorly absorbed in the body have been encapsulated in the cyclodextrin cavity. The enhanced solubility leads to enhanced bioavailability of the drug. Crown ethers can form complexes with potassium ions. Similarly calixarenes form complexes with organic molecules like toluene, benzene in relation to the ring size. Bradshaw, J. S Comprehensive Supramolecular Chemistry. Vol.1, 35, 1996., Odashimo, Koya, K. Comprehensive Supramolecular Chemistry. Vol 2, 143, 1996., Pochini, Ungaro, R. Comprehensive Supramolecular Chemistry. Vol. 2, 103, 1996.) Cyclodextrins are well known cyclic oligosaccharides that can solubilize hydrophobic compounds in aqueous media (Wenz, G. Angew Chem. 106, 851, 1994). The solubilization is effected by complexation of the water insoluble species within the hydrophobic cavity of cyclodextrin. The use of cyclodextrin to dissolve suitable monomers in water has been described in the literature (Storsberg, Ritter, H. Macromolecular. Rapid.
Communications. 21, 230, 2000., Jeromin, Ritter, H. Macromolecular. Rapid.
Communications. 19, 377, 1998., Jeromin, Noll, Ritter, H. Macromolecular.
Chemistry&. Physics 199, 2641-1998., Glockner, Ritter, H. Macromolecular. Rapid.
Communications, 20, 602, 1999). Some patents describe the use of cyclodextrin preferably in catalytic amounts in order to improve emulsion polymerization yields (Lau. WEur. Pat Appl Rohm Haas, 1996, Ger Offen., BASF AG, Ludwigshafen, 1997, US Patent no.
6,225,299, 1 s t May, 2000., US Patent 6,040409, 7 th May, 1998.). But the preparation of host-guest complexes comprising monomers containing multiple unsaturation and cyclic compounds has not been reported till date.
30/11 2006 16:20 FAX 61 3 92438333 GRIFFITH HACK IPAUSTRALIA 1a006/026 Va NO We have surprisingly found that monomers which contain multiple unsaturation form inclusion 0 complexes of varying stoichiometries with cyclodextrins. Further the unsaturated sites z encapsulated within the cyclodextrin cavity do not react with the growing free radical chain.
n The polymerization of inclusion complexes of vinyl monomers containing multiple unsaturation, therefore leads to soluble polymers containing unreacted unsaturated sites.
.4 Once the cyclodextrin is removed from the system, the deprotected, unsaturated site can Sparticipate in polymerization in the second stage and lead to cross linked products having o enhanced mechanical, thermal and solvent resistance characteristics. These polymers therefore, Soffer the ease of processing of thermoplastics and enhanced properties ofthermnnosets.
Objects of the present invention O The principle object of the present invention is to develop inclusion complexes of cyclic macromolecular compounds and monomers comprising multiple unsaturated groups.
Another object of the present invention is to develop a method for the preparation of soluble polymers from the complexes so formed using the free radical polymerization methods.
Summary of the present invention The present invention relates generally to an inclusion complex containing monomers with multiple unsaturation and cyclic macromolecular organic compound represented by the general formula Ax By wherein A is a monomer containing units of vinyl unsaturation and B is a cyclic host compound with repeat units, and also, a process for the preparation of soluble homopolymers with unsaturation group from the inclusion complex, and homopolymers formed from the complex or process.
Detailed description of the present invention Accordingly, the present invention relates generally to an inclusion complex containing monomers with multiple unsaturation and cyclic macromolecular organic compound represented by the general formula Ax By wherein A is a monomer containing units of vinyl unsaturation and B is a cyclic host compound with repeat units, and also, a process for the preparation of soluble homopolymers with unsaturation group from the inclusion complex, and homopolymers formed from the complcx or process.
In an embodiment of the present invention, there is provided an inclusion complex containing monomers bearing multiple unsaturation and cyclic macromolecular organic compound represented by the general formula x 0/l11¢O¢ "ne\qi@I= lsml;\lisogo5sP|l8\Pb^ PJ )^ipLP ;O()3EO4 QC 1O/ll/OG COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30 30/11 2006 16:20 FAX 61 3 92438333 GRIFFITH HACK -,IPAUSTRALIA IR007/026
VO
o6 0 A, By 0 wherein A is a monomer containing units of vinyl unsaturation and B is a cyclic host Z compound with repeat units, wherein l<x< 5 and 3<yC9 respectively, and the ratio of A, to 0 By is in the range of l:0.l to 1:10.
In an embodiment of the present invention the value of'y' is 5<y<9.
In yet another embodiment of the present invention the ratio of Ai to By is in the range of 1:1 to 1:3.
In still another embodiment of the present invention the ratio of Ak to BY is about 1:1.
In still another embodiment of the present invention, the inclusion complex is one that can be converted into organic solvent soluble homopolymers bearing free unsaturated groups by free 0 radical polymerization.
In still another embodiment of the present invention, there is provided a process for the preparation of organic solvent soluble homopolymers with unsaturation group from an inclusion complex as described above, the said process comprising the steps of: Dissolving with stirring cyclic macromolecular organic compound or its derivative in water at ambient temperature, Adding stoichiometrie amount of monomer with multiple unsaturation to the solution of step Stirring the mixture of step at a temperature range of 200 to for a period of 24-28 hours, Separating the complex formed in step Washing the complex of step with water, followed by an organic solvent, Drying the solvent washed complex of step to obtain purified complex, Dissolving the purified complex of step 'T in a polar aprotic solvent, Adding azo or peroxide or photo initiator to the solution of step 'g' under nitrogen purging, Heating the mixture of step at a temperature range of 500 C to C for a period of 16 hrs to 24 hrs, Pouring the reaction mixture of step into water to precipitate the homopolymers, and Separating precipitated homopolymers of step '7 by filtration- In one embodiment, the process comprises the further step of: COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30 30/11 2006 16:21 FAX 61 3 92438333 GRIFFITH HACK IPAUSTRALIA R008/0213 c\O 7 Purifiying the homopolymers of step by dissolving and O reprecipitating the homopolymers in tetrahydrofuran and peterolum Z ether, respectively.
0 SIn still another embodiment of the present invention, wherein in step the cyclic compound is a macromolecular cyclic organic compound selected from a group consisting ofcyclodextrin and its derivatives, crown ethers, cryptands, cyclophanes or their derivatives.
SIn still another embodiment of the present invention, in step the monomer with multiple 0 unsaturation is selected from a group consisting of dimethacrylate, diacrylate, trimethacrylate, V tetramethacrylate such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, vinyl methacrylate, vinyl Sacrylate, glycerol dimethacrylate, glycerol diacrylate, divinyl benzene or bisphenol A dimethacrylate. Other possible monomers are pentaerylthrilol tetraacrylate, penta erythriol trimethacylate, pentaacrythilol tetrametha acrylate, bisphenol, dimethacrylate, glycerol diacrylate, trimethylol, propane acrylate or pentaacrytllrilol tetramethylacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane acrylate or pentacrythrilol tetraacrylate.
In still another embodiment of the present invention, in step the organic solvent is selected from a group consisting of acetone, ethyl alcohol, methanol, tetrahydrofuran or petroleum ether.
In still another embodiment of the present invention, in step the polar aprotic solvent is selected from a group consisting of N, N-dimethyl formamide chloroform or tetrahydrofuran.
Another option is dimethyl sulphoxide.
In still another embodiment of the present invention, in step the azo initiator is selected from the group consisting of 2,2' azobisisobutyronitrile, benzoyl peroxide or tbutylhydrogenporoxide. Potassium persulphate is another option.
In still another embodiment of the present invention, the homopolymcr obtained has unsaturated group present in it.
In still another embodiment of the present invention, the homopolymer obtained is soluble in organic solvent.
In still another embodiment of the present invention, in step the photochemical initiator used is selected from the group consisting of 1-hydroxy cyclohexyl phenyl ketone and benzophenone.
The present invention provides soluble homopolymers of di, tri or tetra functional cross linkers containing unsaturation, and the synthesis thereof. More particularly it relates to the inclusibn complexes comprising monomers with multiple unsaturation, their synthesis and polymerization thereof leading to the preparation of soluble polymers. The process involves preparation of inclusion complexes of the monomers with cyclic organic THm\C«rar \PtBnt\SD00-5SS\P5s936 .ADU\Elp.i\alB35.94 .doe 30/2/oD COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30 WO 2005/014671 PCT/IB2003/003593 8 compounds and subsequent polymerization of the complexes with a suitable polymerization initiator.
This invention relates to inclusion complexes of cyclic macromolecular organic compounds and polymerization thereof. More particularly it relates to the said inclusion complexes, the process for their synthesis and their polymerization. Still more particularly it relates to the complexes comprising cyclodextrins and monomers containing multiple unsaturation sites, the process for the preparation thereof and the synthesis of soluble polymers using these complexes.
The polymers so prepared can be further cast into film, made into microspheres or any desired shape and further converted into cross-linked insoluble products in the second stage. Polymers prepared under identical conditions using conventional methods lead to insoluble products which can not be further cast into fihns or converted into microspheres or any desired shape. The invention includes the preparation of complexes comprising monomers with multiple unsaturations and cyclic organic compounds, as illustrated by cyclodextrins. Polymerization of the complexes is carried out using a suitable free radical initiator. The polymers formed are soluble in common solvents and contain unsaturated groups, which can be further polymerized in a second step.
Accordingly the present invention provides inclusion complexes having general formula AxBy, comprising of monomers containing multiple unsaturation and a cyclic compound, wherein A is a monomer containing number of vinyl unsaturation x where 0<x <5 and wherein B is the cyclic host molecule comprising y units, where 3<y<9 and the ratio of Ax to By varies in the range 1:0.1 to 1:10, The present invention provides a process for the preparation of inclusion complex comprising dissolving a cyclic compound or its derivatives in water at room temperature optionally under agitation, adding stoichiometric amount of the monomer with multiple unsaturation to this solution and stirring the mixture for 24-48 hrs. at temperature in the range 20 0 C to 30 0 C, separating the complex by conventional methods, washing with water, followed by a organic solvent, drying the complex to obtain the inclusion complex.
In yet another embodiments of the present invention the cyclic compound may be a macromolecular organic compound exemplified by cyclodextrin, crown ethers, cryptands, cyclophanes or their derivatives.
In yet another embodiment the monomer may be di, tri or tetra acrylates, exemplified by ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, pentaerythritol tetra WO 2005/014671 PCT/IB2003/003593 9 acrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane acrylate, pentaerythritol tetracrylate, aromatic divinyl compound as exemplified by divinyl benzene.
In another embodiment of the present invention the inclusion complex wherein the monomer is a diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate, tetra methacrylate and aromatic vinyl compounds exemplified by ethylene glycol dimethacrylate, divinyl benzene, trimethylol propane trimethacrylate, pentaerythritol tetra acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane acrylate, pentaerythritol tetraacrylate.
In still another embodiment the solvent used for washing may be aliphatic alcohols ketones or water exemplified by methanol, ethanol, acetone or water.
In still another embodiment the inclusion complexes may be polymerized by dissolving in polar aprotic solvents like N, N dimethyl formamide, dimethyl sulfoxide using azo, redox or peroxide type initiators, exemplified by azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, potassium persulfate.
In still another embodiment the polymerization of the inclusion complexes leads to polymers containing free unsaturated groups and are soluble in organic solvents.
In yet another embodiment the above mentioned soluble polymers containing unsaturated groups can be further polymerized using azo, redox or peroxide type initiators, exemplified by azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, potassium persulfate.
In yet another embodiment the homo polymers prepared as aforesaid contain unsaturated groups and are solvent soluble.
In yet another embodiment the abovementioned soluble polymers containing unsaturated groups can be further polymerized using uv irradiation and photochemical initiators exemplified by 1-hydroxy cyclohexyl phenyl ketone, benzophenone.
The present invention further provides a process for the preparation of homo polymers by the free radical polymerization methods of the inclusion complexes of claim using a suitable free radical initiator.
The invention provides a process for the preparation of soluble homopolymers, which when prepared by conventional polymerization methods lead to cross linked products.
WO 2005/014671 PCT/IB2003/003593 In another embodiment the inclusion complexes which when polymerized lead to polymers containing free unsaturated groups and are soluble in organic solvents.
In still another embodiment the soluble polymers containing unsaturated groups can be further polymerized using azo, redox or peroxide type initiators, exemplified by azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, potassium persulfate.
In a feature of the present invention the conventional methods of polymerization may be: 1. Thermal polymerization in the temperature range 40 0 C to 80 0 C under inert atmosphere.
2. Polymerization by UV irradiation at temperature in the range 4 0 C to 40 0 C using photoinitiators.
3. Polymerization by y irradiation in absence of a free radical initiator.
4. Suspension or emulsion polymerization to obtain the polymer in spherical form.
In another feature the scope of the invention is not restricted to monomers containing multiple unsaturation and cyclodextrin or its derivatives and the compositions of the complexes described above.
In yet another feature the non-solvent for precipitation of soluble homo polymer may be ethers, hexanes or aqueous medium as exemplified by diethyl ether, hexane, petroleum ether, tctrahydrofuran.
The invention is described herein below with reference to examples, which are illustrative only and should not be construed to limit the scope of the present invention in any manner.
Example 1 This example provides the preparation of P-cyclodextrin-ethylene glycol dimethacrylate complex.
11.35 g (0.01 moles) P-cyclodextrin was dissolved in 450 ml distilled water at room temperature. To this 1.98 g (0.01 moles) ethylene glycol dimethacrylate was added in one portion and the mixture was stirred using a magnetic stirrer for 24 hours. The complex precipitated from the solution was filtered under vacuum. The complex was washed thoroughly with distilled water to remove uncomplexed P-cyclodextrin. and with methanol to remove uncomplexed ethylene glycol dimethacrylate. The complex was dried at room temperature in a dessicator. The yield was 75 The complex was characterized by 200 MHz 'H NMR and IR. The stoichiometry of the complex was determined from the area of the protons for B-cyclodextrin and ethylene glycol dimethacrylate and found to be 1:1. IR WO 2005/014671 PCT/IB2003/003593 11 spectroscopy indicated the presence of unsaturation in the complex indicating the formation of inclusion complex of ethylene glycol dimethacrylate and p-cyclodextrin.
Example 2 This example provides the preparation of P-cyclodextrin-divinyl benzene complex.
11.35 g (0.01 moles) P-cyclodextrin was dissolved in 450 ml distilled water at room temperature. To this 1.6g (0.01moles) of 80 1,4 divinyl benzene in ethyl benzene was added and the mixture was stirred at room temperature for 24 hours. The complex comprising 1,4 divinyl benzene and P-cyclodextrin precipitated from the solution This was filtered under vacuum, washed with water and with acetone and dried in a desiccator at room temperature. The yield was 80 The complex was characterized by 'H NMR, IR.
The stoichiometry of the complex was 1: 1 as determined by NMR.
Example 3 This example provides the preparation of p-cyclodextrin-vinyl methacrylate complex.
11.35 g (0.01 moles) P-cyclodextrin was dissolved in 450 ml distilled water at room temperature. To this 1.2 ml (0.01 moles) vinyl methacrylate was added and the mixture was stirred at room temperature for 24 hours. The complex comprising vinyl methacrylate and P-cyclodextrin precipitated from the solution. It was recovered by vacuum filtration.
The complex was washed with water and then with ethanol. The complex was dried at room temperature in a vacuum dessicator. The yield was 80 The complex was characterized by 1 H NMR and IR spectroscopy. The stoichiometry of p-cyclodextrin and vinyl methacrylate in the complex was 1.5 1 as estimated by 1 H NMR.
Example 4 This example provides preparation of y cyclodextrin-ethylene glycol dimethacrylate complex.
y -cyclodextrin 0.648 g (0.0005 moles) was dissolved in 25 ml water. To this 99.2 mg (0.0005 moles) ethylene glycol dimethacrylate was added and the mixture was stirred at room temperature for 24 hours. The complex precipitated as white solid, which was filtered under vacuum and washed with distilled water and subsequently with acetone and dried at room temperature. The yield was 70 Example This example provides the preparation of P-cyclodextrin-trimethylol propane trimethacrylate complex.
WO 2005/014671 PCT/IB2003/003593 11.5 g (0.01 moles) P-cyclodextrin was dissolved in 450 ml distilled water. 3.2 ml (0.01 moles) trimethylol propane trimethacrylate was added to the solution and the mixture was stirred for 24 hours. The complex that precipitated was filtered and washed with water and subsequently with methanol. The yield was 6.7 g (45 The complex was characterized by 'H NMR and IR spectroscopy. The stoichiometry of the complex as determined by proton NMR was 1:1 (trimethylol propane trimethacrylate P-cyclodextrin).
Example 6 This example provides preparation of P-cyclodextrin-trimethylol propane complex.
11.5 g (0.01 moles) 0-cyclodextrin was dissolved in 450 ml distilled water. 1.6 ml (0.005 moles) trimethylol propane trimethacrylate was added to the solution and the mixture was stirred for 24 hours. The complex that precipitated was filtered and washed with water and subsequently with methanol. The yield of the complex was 5.3 g (42 The stoichiometry of the complex as determined by 'H NMR was 1 2 (trimethylol propane trimethacrylate: 0-cyclodextrin).
Example 7 This example provides the preparation of a-cyclodextrin-ethylene glycol dimethacrylate complex.
0.973 g (0.001 moles) ac-cyclodextrin was dissolved in 25 ml water. To this 0.198g (0.001 moles) ethylene glycol dimethacrylate was added and the mixture stirred for 36 hours at room temperature. White solid precipitated and was filtered and washed with water. The yield was 6 The complex was characterized by 'H NMR and IR spectroscopy.
Example 8 This example provides the preparation ofpoly( divinyl benzene).
1 g complex of divinyl benzene and P-cyclodextrin as described in example 2 was dissolved in 6ml N, N dimethyl formamide in a 20ml glass tube. 10 mg azobisisobutyronitrile was added and the test tube was flushed with nitrogen for 10-15 minutes. The test tube was immersed in a water bath maintained at 65C. The polymerization was carried out for 18 hours. After cooling, the solution was added to ml water with stirring. P-cyclodextrin remained in the aqueous layer and the polymer was isolated by filtration The yield of the polymer was 58%.
Example 9 This example provides the preparation ofpoly(ethylene glycol dimethacrylate, EGDMA WO 2005/014671 PCT/IB2003/003593 1g ethylene glycol dimethacrylate P-cyclodextrin complex as described in example 1 was dissolved in 6 ml N, N dimethyl formamide in test tube. 10 mg azobisisobutyronitrile was added and the test tube was flushed with nitrogen for 15 min. The polymerization was carried out for 20 hours at 65C. The polymer solution was poured in 80 ml distilled water to precipitate the polymer. Polymer was filtered and dried under vacuum at room temperature. The yield of the polymer was 68 The structure was confirmed by 'H NMR and IR spectroscopy. 1H NMR showed presence of vinyl unsaturation. This was also confirmed by IR spectroscopy. The molecular wt of the polymer as characterized by GPC was Mw= 1,00754, Mn= 20,932 and the polydispersity was 4.8.
Example This example provides the second step polymerization ofpoly(EGDMA).
0.1 g poly(EGDMA) prepared according to example 9, was dissolved in 8 2 (dimethyl sulfoxide dichloromethane) and 5 mg photo initiator 1-hydroxy cyclohexyl phenyl ketone was added. The solution was purged with nitrogen for 10 minutes and exposed to UV irradiation for 20 minutes. The polymer was crosslinked and formed a gel in the solvent mixture. This is an indirect evidence for the selective polymerization of one vinyl group in the first stage followed by a second stage polymerization leading to network formation.
Comparative example (a) Ig ethylene glycol dimethacrylate was dissolved in 5 ml N, N dimethyl formamide in a test tube. To this 10mg azobisisobutyronitrile was added and the test tube was purged with nitrogen for 15 min. The polymerization was carried out for 18 h at 65 0 C. The polymer was obtained as a crosslinked gel that was insoluble in common organic solvents like chloroform, acetone, and methanol.
Comparative example (b) Ethylene glycol dimethacrylate 0.2 g (Immoles) and 1.14 g p-cyclodextrin (Immole) was dissolved in 5 ml N, N dimethyl formamide. To this 5 mg azobisisobutyronitrile was added and nitrogen was bubbled for 10 minutes. The polymerization was carried out at 65 0 C for 16 hours. The polymer was obtained as a crosslinked gel that was insoluble.
Example 11 This example provides the photopolymerization of P-cyclodextrin-EGDMA complex.
1 g ethylene glycol dimethacrylate P-cyclodextrin complex prepared as in example 1 was dissolved in 6 ml N, N dimethyl formamide in test tube. 10 mg 1-hydroxy cyclohexyl phenyl ketone was added and the test tube was flushed with nitrogen for 15 min. The 30/11 2008 16:21 FAX 61 3 32438333 GRIFFITH HACK IPAUSTRALIA R009/026 14 polymerizaton was carried out for 15 minutes at room temperature by exposure to UV irradiation. The polymer solution was poured in 80 ml distilled water. Polymer was filtered and dried under vacuum at room temperature. The yield of the polymer was 55%. The structure was confirmed by 11 NMR and IR spectroscopy. 11-J NMR showed presence of vinyl unsaturation. This was also confirmed by I spectroscopy.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e.
to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30
Claims (10)
- 3. An inclusion complex of claim 1 or claim 2, wherein the ratio of A. to By is in the range of to 1;3.
- 4. An inclusion complex of claim 1, which can be converted into organic solvent soluble homopolymers bearing free unsaturated groups, by free radical polymerization.
- 5. A process for the preparation of organic solvent soluble homopolymers with unsaturation group from an inclusion complex of any one of the claims 1 to 4, the said process comprising the steps of: Dissolving with stirring cyclic macromolecular organic compound or its derivative in water at ambient temperature, Adding stoichiometric amount of monomer with multiple unsaturation to the solution of step Stirring the mixture of step at a temperature range of 20* to 30 C for a period of 24-28 hours, Separating the complex formed in step Washing the complex of step with water, followed by an organic solvent, Drying the solvent washed complex of step to obtain purified complex, Dissolving the purified complex of step 'f in a polar aprotic solvent, Adding azo or peroxide or photo initiator to the solution of step 'g' under nitrogen purging, Ml\IlBaUrn nh\( as\sp |oBoe\59s00-S> i\pS9 ,Ag\9co±i\azboa0d .da C30/1110/4 COMSIDNo:SBMI1-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30 30/11 2006 18:22 FAX 61 3 92438333 GRIFFITH HACK IPAUSTRALIA 1 011/026 VN 16 0 S(i) Heating the mixture of step at a temperature range of 50° C to O C for a period of 16 hrs to 24 hrs, S(j) Pouring the reaction mixture of step into water to precipitate the 0 homopolymers, and Separating precipitated homopolymers of step by filtration. S7. A process of claim 6, comprising the step of: 0 t Purifiying the homopolymers of step by dissolving and C, 10 reprecipitating the homopolymers in tetrahydrofuran and peterolum Sether, respectively.
- 8. A process of claim 6 or claim 7, wherein in step the cyclic compound is a macromolecular cyclic organic compound selected from a group consisting ofcyclodextrin, cyolodextrin derivatives, crown ethers, cryptands, cyclophanes or their derivatives.
- 9. A process of any one of claims 6 to 8, wherein in step the monomer with multiple unsaturation is selected from a group consisting of dimethacrylate, diacrylate, trimethacrylate, tetramethacrylate such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, vinyl methacrylate, vinyl acrylate, glycerol dimethacrylate, glycerol diacrylate, divinyl benzene or bisphenol A dimethacrylate, A process of anyone of claims 6 to 9 wherein in step the organic solvent is selected from the group consisting of acetone, ethyl alcohol, methanol, terrahydrofuran or petroleum ether. I1. A process of any one of claims 6 to 10, wherein in step the polar aprotic solvent is selected from a group consisting of N, N-dimethyl formamide, chloroform or tetrahydrofuran.
- 12. A process of any one of claims 6 to 11, wherein in step the azo initiator is selected from the group consisting of 2,2' azobisisobutyronitrile, benzoyl peroxide, t-butyl hydrogen peroxide.
- 13. A process of any one of claims 6 to 11, wherein in step the photo initiator used is selected from the group consisting of 1-hydroxy cyclohexyl phenyl ketone or N=\Mllboull e\Ceh a \Pae ent\o,5900.0-Ib$ P\p 93t .AU\BpnciB\210.D3 49 a/311/ 6 COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30 30/11 2006 16:22 FAX 61 3 32438333 GRIFFITH HACK IPAUSTRALIA R012/026 benzophenone.
- 14. A process of any one of claims 6 to 13, wherein the homopolymer obtained in step has unsaturated group present in it. A process of any one of claims 6 to 14, wherein in step the homopolymer obtained is soluble in organic solvent,
- 16. An organic solvent soluble hornopolymer formed from the inclusion complex of any one of claims I to 4, or from the process of any one of claims 5 to 1
- 17. An inclusion complex, a process for the preparation of an organic solvent soluble homopolymer, or an organic solvent soluble homopolymer as claimed in any one of the preceding claims and substantially as herein described with reference to the examples. N|\MelbrUr[\tiBEdsn\Pat.Bnt\pg5s-99g\S9g3.Alappff;;t\pp 3 5 M pg, 0 c 3D/t2/O4i COMS ID No: SBMI-05523450 Received by IP Australia: Time 16:31 Date 2006-11-30
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IB2003/003593 WO2005014671A1 (en) | 2003-08-12 | 2003-08-12 | Inclusion complexes of cyclic macromolecular organic compounds and polymerization thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2003250494A2 true AU2003250494A2 (en) | 2005-02-25 |
| AU2003250494A1 AU2003250494A1 (en) | 2005-02-25 |
Family
ID=34131111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2003250494A Abandoned AU2003250494A1 (en) | 2003-08-12 | 2003-08-12 | Inclusion complexes of cyclic macromolecular organic compounds and polymerization thereof |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1656399A1 (en) |
| JP (1) | JP2007516300A (en) |
| AU (1) | AU2003250494A1 (en) |
| WO (1) | WO2005014671A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070122375A1 (en) * | 2005-09-12 | 2007-05-31 | Council Of Scientific And Industrial Research | Bile acid sequestrant and process for preparation thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5792821A (en) * | 1997-01-06 | 1998-08-11 | American Dental Association Health Foundation | Polymerizable cyclodextrin derivatives |
| EP1247820B1 (en) * | 2001-03-29 | 2008-02-27 | Agfa Graphics N.V. | Method of preparing polymer particles having narrow particle size distribution |
| AU4888702A (en) * | 2001-07-02 | 2003-01-09 | Rohm And Haas Company | Water resistant compositions that retain active components and process |
-
2003
- 2003-08-12 AU AU2003250494A patent/AU2003250494A1/en not_active Abandoned
- 2003-08-12 WO PCT/IB2003/003593 patent/WO2005014671A1/en active Application Filing
- 2003-08-12 EP EP03817976A patent/EP1656399A1/en not_active Withdrawn
- 2003-08-12 JP JP2005507564A patent/JP2007516300A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007516300A (en) | 2007-06-21 |
| WO2005014671A1 (en) | 2005-02-17 |
| AU2003250494A1 (en) | 2005-02-25 |
| EP1656399A1 (en) | 2006-05-17 |
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