US20050096443A1 - Soluble polymers comprising unsaturation and process for preparation thereof - Google Patents
Soluble polymers comprising unsaturation and process for preparation thereof Download PDFInfo
- Publication number
- US20050096443A1 US20050096443A1 US10/700,511 US70051103A US2005096443A1 US 20050096443 A1 US20050096443 A1 US 20050096443A1 US 70051103 A US70051103 A US 70051103A US 2005096443 A1 US2005096443 A1 US 2005096443A1
- Authority
- US
- United States
- Prior art keywords
- methacrylate
- vinyl
- unsaturation
- initiator
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 229920002521 macromolecule Polymers 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 55
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 30
- 229920000858 Cyclodextrin Polymers 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- -1 2-hydroxyl propyl Chemical group 0.000 claims description 10
- 239000001116 FEMA 4028 Substances 0.000 claims description 10
- 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 claims description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 10
- 229960004853 betadex Drugs 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920006037 cross link polymer Polymers 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- FTWHFXMUJQRNBK-UHFFFAOYSA-N alpha-Methylen-gamma-aminobuttersaeure Natural products NCCC(=C)C(O)=O FTWHFXMUJQRNBK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 claims description 3
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003880 polar aprotic solvent Substances 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 3
- 239000011541 reaction mixture Substances 0.000 claims 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 2
- IFBMOBFQBJZBMV-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphanyl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C IFBMOBFQBJZBMV-UHFFFAOYSA-N 0.000 claims 2
- 150000003926 acrylamides Chemical class 0.000 claims 2
- 229960003328 benzoyl peroxide Drugs 0.000 claims 2
- 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 2
- 125000004386 diacrylate group Chemical group 0.000 claims 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 claims 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims 1
- YCIGYTFKOXGYTA-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)butanenitrile Chemical compound N#CCCCN=NCCCC#N YCIGYTFKOXGYTA-UHFFFAOYSA-N 0.000 claims 1
- 239000004160 Ammonium persulphate Substances 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000004159 Potassium persulphate Substances 0.000 claims 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 1
- 235000019395 ammonium persulphate Nutrition 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 239000012966 redox initiator Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 30
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000011859 microparticle Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 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 17
- 238000004566 IR spectroscopy Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 102100026735 Coagulation factor VIII Human genes 0.000 description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
- 229940097362 cyclodextrins Drugs 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LGTWBUAVHCCEAR-UHFFFAOYSA-N 2-ethenylpyridine methyl 2-methylprop-2-enoate 2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCOC(C(=C)C)=O.C(=C)C1=NC=CC=C1.C(C(=C)C)(=O)OC LGTWBUAVHCCEAR-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910016455 AlBN Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000001074 Langmuir--Blodgett assembly Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 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 description 1
- IQIXQINTSRHNDE-UHFFFAOYSA-N butanimidamide;dihydrochloride Chemical compound Cl.Cl.CCCC(N)=N IQIXQINTSRHNDE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000004851 dental resin Substances 0.000 description 1
- 210000004268 dentin Anatomy 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
Definitions
- the said patent deals with functionalized polymers containing cyclodextrin wherein cyclodextrin are covalently bonded to a monomer that the polymer structure contains cyclodextrin.
- the subject matter of the invention covered by this patent is a highly substituted or derivatized cyclodextrin containing unsaturated groups.
- Another feature of this invention is presence of a functionalized group in the polymer structure which can form hydrogen bonds, ionic bonds, Van der Waal interactions with appropriate substrate so as to enhance adhesion.
- the invention also covers photo sensitive initiators, which are encapsulated in cyclodextrin.
- the invention thus deals with complexes of thermal initiators encapsulated in cyclodextrin derivatives. In many cases the functional sites such as carboxyl groups present in the polymer are bridged using calcium or other di-cationic metals so as to provide cross linking.
- the subject matter of our invention deals with the encapsulation of the cross linker which can contain more than one unsaturated groups. It may be noted here that the interaction between the cross linker and cyclodextrin exploited in this work is non-covalent in nature. As a result of that complexation, vinyl groups present in the cross linker but encapsulated in the cyclodextrin cavity do not take part in polymerization and prevent cross-linking. Also, cyclodextrin can be removed after polymer has been formed and is not a part of the resulting polymer structure after the second stage of cross linking is effected either by thermal or photo chemical polymerization. It may be further mentioned that the initiators used by us are in their free form and are not encapsulated in cyclodextrin.
- unsaturated groups are incorporated into these copolymers, they can then be converted into films, membranes or micro or nanoparticles and can be crosslinked in a second step.
- Such polymers would find applications in electronics, photoresists, controlled release delivery systems, micro electro mechanical systems (MEMS) etc.
- the inclusion complex may be a monomer containing multiple unsaturation such as di, tri or tetra acrylates or methacrylates as exemplified by ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate or aromatic divinyl compounds as exemplified by divinyl benzene.
- ethylene glycol dimethacrylate trimethylol propane trimethacrylate, dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate or aromatic divinyl compounds as exemplified by divinyl benzene.
- This example provides the preparation of p(methyl methacrylate-co-ethylene glycol dimethacrylate (EGDMA)).
- This example provides the preparation of p(methyl methacrylate-co-trimethylol propane trimethacrylate (TRIM)).
- Methyl methacrylate 1 g (9.9 mmoles), 0.156 g (1.98 mmoles) vinyl pyridine and 0.4 g (0.297 mmoles) ( ⁇ -cyclodextrin-ethylene grycol dimethacrylate complex were dissolved in 5 ml DMF. 10 mg azobisiobutyronitrile was added and the test tube was purged with nitrogen for 15 minutes. Polymerization was carried out for 65° C. for 18 h. The polymer was obtain d by precipitation in water. The yield of the polymer was 78%.
- the polymer was characterized by 1 H NMR and IR spectroscopy 1 H NMR (DMSOd 6 ): 3.6 ⁇ , —OCH3, 0.9-1.9 ⁇ —(CH—CH 2 )—, 7.22, 8.49 ⁇ pyridine protons, 4.03 ⁇ , 5.5 ⁇ , ⁇ CH2.
- the polymer was insoluble in THF but dissolved in a mixture of tetrahydrofuran/isopropanol 50:50 v/v.
- the polymer had an equilibrium swelling of 71% in buffer of pH 2 and negligible swelling at pH 5.8
- Acrylic acid g (0.01387 mole), 0.555 g (0.4 mmoles) ⁇ -cyclodextrin-ethylene glycol dimethacrylate complex was dissolved in 5 ml N, N dimethyl formamide. 10 mg azobisisobutyronitrile was added as the initiator and test tube is purged with nitrogen for 15 mins. Polymerization was carried out at 65° C. for 18 hr. The polymer is obtained by precipitation in methanol. ⁇ -cyclodextrin is insoluble in methanol and can be recovered while poly (acrylic acid is soluble in methanol. The polymer was characterized by NMR and IR spectroscopy.
- the polymer was characterized by IR and 1 H NMR spectroscopy 1 H NMR (D 2 O): 0.9-1.2 ⁇ , (—CH—CH 2 )—, 2.93 ⁇ , —CH 3 , 3.5 ⁇ , m, —CH, 4.03 ⁇ , EDA protons, 6.2 ⁇ —NH.
Abstract
The present invention describes the synthesis of soluble copolymers containing multiple unsaturations. These copolymers contain reactive vinyl groups which can be further reacted in a second stage polymerization. The process involves copolymerization of a vinyl monomer with an inclusion complex of a monomer having multiple unsaturations and a cyclic macromolecular compound to yield soluble polymers. These polymers may be cast into films, membranes or may be converted in micro or nanoparticles and then crosslinked in a second step polymerization.
Description
- The present invention relates to soluble copolymers comprising unsaturation and a process for the preparation thereof. More particularly it relates to polymers of the formula [(Ax)(By)]n, wherein A is any vinyl monomer comprising one unsaturation, B is any vinyl monomer containing multiple unsaturation and x, y and n are any integral values greater than zero. In our co-pending application No. NCL-28-2002 (PCT Application No. PCT/IB03/03593) we have described the process for the preparation of inclusion complexes of cyclic macromolecular compounds with monomers containing multiple unsaturation Polymerization of such complexes with vinyl substituted monomers yields polymers that are soluble and have unsaturated sites for further modification.
- Thermosetting polymers can not 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 certain thermosetting polymers, reactive groups are introduced in the backbone. 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. These resins attain their desired properties i.e., insolubility in most organic solvents, good water resistance and hardness by network formation and are used as coatings. (Van E. S. J. J. in Polymeric Dispersions Principles and Applications. Asua, J. M. (Ed). Kluwer Publishers, 1997, p. 451; Ooka, M. Ozawa, H. Progress in Organic Coatings, vol. 23, 1994, p. 325). The need for polymers which are water 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 different fields.
- Water insoluble molecules become water-soluble on treatment with aqueous solutions of cyclodextrins or similar best molecule. The inclusion phenomenon leads to significant changes of solution properties and reactivity of the guest molecule. The formation of inclusion complexes of hydrophobic monomers with β-cyclodextrin or its derivatives has been reported. (Storsberg, J., Ritter, H. Macromolecular Communications. 21, 230, 2000. Jeromin, J. Ritter, H. Macromolecular Communications. 19, 377, 1998. Jeromin, J. Noll, O. Ritter, H. Macromolecular Chemistry & Physics, 199, 2641-1998. Glockner, P. Ritter, H. Macromolecular Rapid. Communications, 20, 602, 1999). It has been established that the reactivity ratios of complexed monomers differ significantly from those of the uncomplexed monomers.
- Complexes of cyclodextrin have been investigated in the past. U.S. Pat. No. 4,906,488 describes these for the release of permeants to the outside host. Similarly U.S. Pat. No. 5,258,414 describes encapsulation of blowing agents into cyclodextrins and incorporation of the complexes into thermoplastics for delayed release of the blowing agents. U.S. Pat. No. 5,268,286 describes the method for polymerization of biocatalysts on polymers. Similarly U.S. Pat. No. 5,290,831 describes the use of cyclodextrins for stabilization of the polymerization initiators as to regulate the polymerization in a desirable manner.
- U.S. Pat. No. 6,180,739 describes polymerizable cyclodextrin derivatives for applications in dental resins, which adhere strongly to dentin The said patent covers polymerizable cyclodextrin derivatives wherein cyclodextrin is reacted with a large excess of monomer so that each cyclodextrin molecule is covalently linked to a large number of polymerizable groups. The compositions are useful in dental and industrial formulation. Another feature of this invention is the presence of functional groups in the polymer structure which can form hydrogen bonds, ionic bonds, Van der Waal interactions with the appropriate substrate so as to enhance adhesion. The invention also covers initiators, which are encapsulated in cyclodextrin structure. The cyclodextrin is an integral part of the polymer structure and has a functional role in application.
- The said patent deals with functionalized polymers containing cyclodextrin wherein cyclodextrin are covalently bonded to a monomer that the polymer structure contains cyclodextrin. Thus the subject matter of the invention covered by this patent is a highly substituted or derivatized cyclodextrin containing unsaturated groups. Another feature of this invention is presence of a functionalized group in the polymer structure which can form hydrogen bonds, ionic bonds, Van der Waal interactions with appropriate substrate so as to enhance adhesion. The invention also covers photo sensitive initiators, which are encapsulated in cyclodextrin. The invention thus deals with complexes of thermal initiators encapsulated in cyclodextrin derivatives. In many cases the functional sites such as carboxyl groups present in the polymer are bridged using calcium or other di-cationic metals so as to provide cross linking.
- The subject matter of our invention deals with the encapsulation of the cross linker which can contain more than one unsaturated groups. It may be noted here that the interaction between the cross linker and cyclodextrin exploited in this work is non-covalent in nature. As a result of that complexation, vinyl groups present in the cross linker but encapsulated in the cyclodextrin cavity do not take part in polymerization and prevent cross-linking. Also, cyclodextrin can be removed after polymer has been formed and is not a part of the resulting polymer structure after the second stage of cross linking is effected either by thermal or photo chemical polymerization. It may be further mentioned that the initiators used by us are in their free form and are not encapsulated in cyclodextrin.
- In our copending application No. NCL-28-2002 (PCT Application No. PCT/IB03/03593) we have described the preparation of inclusion complexes of cyclodextrins with monomers containing multiple unsaturations. Polymerization of these complexes gives rise to soluble homopolymers containing unsaturated sites which can be further crosslinked. But applications of homopolymers of monomers having multiple unsaturations are limited. Copolymerization of different monomers gives rise to tailor made materials for a wide range of applications. Depending upon the composition of the comonomers either hydrophilic, hydrophobic or amphiphilic polymers can be synthesized. If unsaturated groups are incorporated into these copolymers, they can then be converted into films, membranes or micro or nanoparticles and can be crosslinked in a second step. Such polymers would find applications in electronics, photoresists, controlled release delivery systems, micro electro mechanical systems (MEMS) etc.
- The principle object of the present invention is to provide soluble copolymers of vinyl monomers containing multiple unsaturations and a process for the preparation thereof.
- Another object is to provide a new process for the preparation of crosslinked polymers in different forms like thin films, membranes, monolayers, micro or nanoparticles in the second step polymerization.
- Accordingly, the present invention provides soluble copolymers having a general formula [(Ax)(By)]n, wherein A is any vinyl monomer comprising one unsaturation, B is any vinyl monomer containing multiple unsaturation and x, y and n are any integral values greater than zero. The present invention also provides a process for preparation of soluble copolymers which comprises dissolving an inclusion complex of the monomer containing multiple unsaturation with a cyclic macromolecular compound in an appropriate solvent, adding at least one vinyl monomer and a free radical initiator to this solution and polymerizing by the composition by either thermally or photochemically initiated polymerization in the presence of appropriate initiators to obtain the product.
- In one of the embodiments of the present invention the inclusion complexes are prepared as per the process claimed and described in our copending Application No. NCL-28-2002 (PCT Application No. PCT/IB03/03593).
- In another embodiment the content of the inclusion complex containing multiple unsaturation may be varied from 0.01 to 99.9%.
- In yet another embodiment, the solvent for preparing solution of inclusion complex may be chosen from polar aprotic solvents exemplified by N, N dimethyl formamide, N, N dimethyl acelamide, dimethyl sulfoxide and water.
- In still another embodiment the vinyl monomer may be methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyl propyl methacrylate, 2-amino ethyl acrylate hydrochloride, butyl acrylate, cetyl acrylate, cetyl methacrylate, phenyl methacrylate, N-isopropyl acrylamide, acrylamide, N-t-butyl acrylamide, styrene and styrene sulfonic acid, allyl amine and/or its salts
- In another embodiment the inclusion complex may be a monomer containing multiple unsaturation such as di, tri or tetra acrylates or methacrylates as exemplified by ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate or aromatic divinyl compounds as exemplified by divinyl benzene.
- In yet another embodiment the polymerization initiator may be chosen from azo, peroxide or redox type as exemplified by azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, potassium persulfate, ammonium persulfite.
- In yet another embodiment the initiator may be chosen from a family of water soluble azoinitiators as exemplified by azobis (amidinopropane) dihydrochloride
- In yet another embodiment the soluble copolymers prepared are crosslinked using conventional free radical polymerization methods to give insoluble polymers.
- In one of the features of the present invention the polymerization is carried out by any of the conventional methods of polymerization given below.
-
- i) Thermal polymerization in the temperature range 40° C. to 80° C. under inert atmosphere
- ii) Polymerization by UV irradiation at temperature in the range 4° C. to 40° C. using photoinitiators.
- iii) Polymerization by y irradiation in absence of a free radical initiator.
- iv) Suspension or emulsion polymerization to obtain the polymer in spherical form.
- In a feature of the present invention the copolymers prepared using the described above are soluble in organic solvents and contain unsaturated groups.
- The invention is now described below by examples, which are illustrative but do not limit the scope of the invention.
- This example provides the preparation of β-cyclodextrin-ethylene glycol dimethacrylate complex described in our co-pending application NCL-28-2002 (PCT Application No. PCT/IB03/03593). 11.35 g (0.01 moles) (β-cyclodextrin was dissolved in 450 ml distilled water at room temperature. To this 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 β-cyclodextrin, and with methanol to remove uncomplexed ethylene glycol dimethacrylate. The complex was dried at room temperature in desiccators. The yield was 73%. The complex was characterized by 200 MHz. 1H NMR and IR The stoichiometry of the complex was determined from the area of the protons for β-cyclodextrin and ethylene glycol dimethacrylate and found to be 1:1 IR spectroscopy indicated the presence of unsaturation in the complex indicating toe formation of inclusion complex of ethylene glycol dimethacrylate and β-cyclodextrin.
- This example provides the preparation of p(methyl methacrylate-co-ethylene glycol dimethacrylate (EGDMA)).
- 0.660 g (0.495 mmoles) β-cyclodextrin-ethylene glycol dimethacrylate complex, g methyl methacrylate (9.9 mmoles) was dissolved in 5 ml N, N dimethyl formamide. To this 10 mg azobisisobutyronitrile was added and the tube was purged with nitrogen and dipped in a water bath maintained at 65° C. for 18-20 hours. The polymer was precipitated in water to remove P-cyclodextrin, which remains in the aqueous medium. It was dried in a desiccator at room temperature. The yield was 68%. The polymer was characterized by 1H NMR and IR spectroscopy. Both the methods showed the presence of unsaturation. 1H NMR (CDCl3): 3.6 δ, b, OCH3, 5.97, 6.17 δ, 2H, ═CH2, 4.00 δ, —CH2 of EDA, 8 δ, s-CH3, 0.85, 1.03 δ-CH2—CH). IR 728 cm C═O, 1654 cm′1 —C═C—, 2854, 2926 cm′1 —CH3, 1435 cm′1 ═CH2. The molecular wt as determined by GPC was 88,000.
- This example shows the comparison of polymerization using a preformed complex describe in the process above and by a conventional technique in the presence of (3-cyclodextrin. 1 g methyl methylate (9.9 mmoles), 0.098 g ethylene glycol dimethacrylate (0.49 mmoles) and 0.562 g (0.49 mmoles) β-cyclodextrin were dissolved in 6 ml N, N dimethyl formamide. 10 mg azobisisobutyronitrile was added and the tube was purged with nitrogen for 10 minutes. The polymerization was carried out at 65° C. for 20 hours. The polymer was obtained in the form of an insoluble gel.
- This example provides the preparation of p(methyl methacrylate-co-vinyl methacrylate). 1 g methyl methacrylate (9.9 mmoles), 0.617 g (0.495 mmoles) β-cyclodextrin-vinyl methacrylate complex were dissolved in 5 ml DMF. 10 mg azobisisobutyronitrile was added and the test tube was purged with nitrogen for 20 minutes. The polymerization was carried out 65° C. for 18 hours. Polymer was obtained by precipitating in water. The polymer yield was 70% and the molecular wt as characterized by GPC was 32,300 and polydispersity 6.5. The polymer was characterized by 1H NMR and IR spectroscopy. 1HNMR (CDCl3): 3.57 δ, b, —OCH3, 5.16, 6.17 67 , ═CH 2 of VMA, 1.8 δ —CH3, 0.82, 0.92 &—CH—CH2). IR 728 cm C═O, 1646 cm C═C, 2854, 2926 cm−1 CH3, 1435 cm−1 ═CH2.
- This example provides the preparation of β(vinyl acetate-co-vinyl methacrylate). 1 g (11.6 mmoles), vinyl acetate, 0.724 g (0.59 mmoles) β-cyclodextrin-vinyl methacrylate complex was dissolved in 5 ml DMF. To this 10 mg AlBN was added and the test tube was purged with nitrogen for 15 minutes. Polymerization was carried out at 65° C. for 18 hours. The polymer was isolated by precipitation in water. The yield obtained was 72% and the molecular wt was 4500. The polymer was characterized by 1HNMR and IR spectroscopy.
- This example provides the preparation of p(vinyl acetate-co-ethylene glycol dimethacrylate (EGDMA)).
- 1 g (11.6 mmoles) vinyl acetate, 0.773 β-cyclodextrin-ethylene glycol dimethacrylate complex were dissolved in 5 ml DMF. To this 10 mg AIBN was added and the polymerization was carried out at 65° C. for 18 hours. Polymer was obtained by precipitation in water. The yield was 74%. Molecular wt of the polymer was 4335. The polymer was characterized by 1H NMR and IR spectroscopy. 1H NMR (CDCl3) 2.05 δ, b, —CH3 of vinyl acetate. 79 fi(CH2—CH), 4.08 δ, d, —CH2 of EDA, 5.58, 6.08 δ s, —CHj. IR (nujol) 1720 cm−1, C═O, 1643 cm−1 C═C, 606 cm 947 cm−1 1022 cm−1, 1238 cm−1, 2856, 2924 cm−1 —CH3.
- This example provides the preparation of p(methyl methacrylate-co-trimethylol propane trimethacrylate (TRIM)).
- 1 g methyl methacrylate (9.9 mmoles) and 0.73 g (β-cyclodextrin-trimethylol propane trimethacrylate (TRIM) complex {1:2} was dissolved in 5 ml DMF. To this 10 mg AIBN was added and the test tube was purged with nitrogen for 10 minutes. Polymerization was carried out at 65° C. for 20 h and the polymer was obtained by precipitation in water. The yield was 69%. The molecular wt. of the polymer measured by GPC was 40,200 and the polydispersity 9.2. The polymer was characterized by 1H NMR and IR spectroscopy. 1H NMR (CDCl3): 3.6 δOCH3 of methyl methacrylate, 5.9, 6.15 δ, d, ═CH2 1.97 δ, —CH3, 2.75 2.92 δ, —CH2—O IR (nujol): 1728 cm−1, C═O, 1672 cm−1, 1435 cm−1 ═CH2. 2927 cm−1, 2950 cm−1 —CH3.
- This example provides the preparation of p(methyl methacrylate-co-ethylene glycol dimethacrylate (EGDMA)} by photopolymerization.
- 0.5 g methyl methacrylate (4.95 mmoles) and 0.33 g (0.25 mmoles) p-cyclodextrin-ethylene glycol dimethacrylate complex were dissolved in 2 ml dimethyl formamide. To this 5 mg 1-hydroxy cyclohexyl phenyl ketone was added and the solution exposed to UV irradiation at room temperature for 20 minutes. The polymer was obtained by precipitation in water. The yield was 60%. The polymer was characterized by 1H NMR and IR spectroscopy. The molecular wt of the polymer was Mw=6530, Mn′=2490 and polydispersity 2.6.
- This example provides the preparation of p(methyl methacrylate-co-ethylene glycol dimethacrylate).
- 2 g (0.0198 moles) methyl methacrylate and 5.3 g (3.9 mmoles) β-cyclodextrin-ethylene glycol dimethacrylate were dissolved in 20 ml N, N dimethyl formamide. To this 20 mg azobisisobutyronitrile was added and the polymerization was carried out at 65° C. for 20 h. The polymer was obtained by precipitation in water. The yield was 74%. The molecular wt of the polymer as determined by GPC was Mw=42,000. Mn=19,700, Mw/Mn=2.1. The polymer was characterized by 1H NMR and IR spectroscopy
- This example provides the preparation of p(methyl methacrylate-co-EGDMA) using β-cyclodextrin-EGDMA complex
- Methyl methacrylate, 0.47 g (4.67 mmoles), 0.350 g (0.23 mmoles) β-cyclodextrin-EGDMA complex was dissolved in 3 ml N, N dimethyl formamide and 5 mg azobisisobutyronitrile was added. The test tube was purged with nitrogen for 15 minutes and the polymerization was carried out at 65° C. for 18 hours. The polymer was precipitated in water. It was purified by dissolving in 10 ml dichloromethane filtering and evaporating the dichloromethane. The yield of the polymer was 64%. The polymer was characterized by *H NMR and IR spectroscopy. The molecular weight of the polymer as characterized by GPC was Mw=29,900, Mn=11,340 and polydispersity 2.6.
- This example provides the preparation of p(methyl methacrylate-vinyl pyridine ethylene glycol dimethacrylate
- Methyl methacrylate 1 g (9.9 mmoles), 0.156 g (1.98 mmoles) vinyl pyridine and 0.4 g (0.297 mmoles) (β-cyclodextrin-ethylene grycol dimethacrylate complex were dissolved in 5 ml DMF. 10 mg azobisiobutyronitrile was added and the test tube was purged with nitrogen for 15 minutes. Polymerization was carried out for 65° C. for 18 h. The polymer was obtain d by precipitation in water. The yield of the polymer was 78%. The polymer was characterized by 1H NMR and IR spectroscopy 1H NMR (DMSOd6): 3.6 δ, —OCH3, 0.9-1.9 δ —(CH—CH2)—, 7.22, 8.49 δ pyridine protons, 4.03 δ, 5.5 δ, ═CH2. The polymer was insoluble in THF but dissolved in a mixture of tetrahydrofuran/isopropanol 50:50 v/v. The polymer had an equilibrium swelling of 71% in buffer of pH 2 and negligible swelling at pH 5.8
- This example provides the preparation of p(acrylic acid-co-ethylene glycol dimethacrylate (EGDMA)).
- Acrylic acid g (0.01387 mole), 0.555 g (0.4 mmoles) β-cyclodextrin-ethylene glycol dimethacrylate complex was dissolved in 5 ml N, N dimethyl formamide. 10 mg azobisisobutyronitrile was added as the initiator and test tube is purged with nitrogen for 15 mins. Polymerization was carried out at 65° C. for 18 hr. The polymer is obtained by precipitation in methanol. β-cyclodextrin is insoluble in methanol and can be recovered while poly (acrylic acid is soluble in methanol. The polymer was characterized by NMR and IR spectroscopy.
- This example provides the preparation of p(acrylonitrile-co-ethylene) glycol dimethacrylate (EGDMA)).
- Acrylonitrile 1 g, 5.03 g (3.7 mmoles) (β-cyclodextrin-ethylene glycol dimethaaylate complex was dissolved in 20 ml N, M dimethyl formamide. 16 mg azobisiobutyronitrile was added and the solution was purged with nitrogen for 15 minutes. Polymerization was carried out at 65° C. for 20 h. The polymer was obtained by precipitation in water. The yield of the polymer was 70%. The polymer was characterized by IR and 1H NMR spectroscopy. IR (nujol): 2243 cm−1 —C═N, 1728 cm1, —C═O, 1645 cm−1, ═CH2.
- This example provides the preparation of crosslinked Langmuir Blodgett film1 Poly(methyl methacrylate-EGDMA) containing 20 mol % EGDMA prepared as described in example 8 was dissolved in dichloromethane along with -hydroxy cyclohexyl phenyl ketone as a photoinitiator and cast as thin film on a silicon wafer using the Langmuir-Blodgett technique. The polymer was then crosslinked using UV irradiation giving a crosslinked thin film.
- This example provides the preparation of p(N-isopropyl acrylamide-co-ethylene glycol dimethacrylate)
- 1 g N-isopropyl acrylamide (8.8 mmoles) 0.589 g (0.44 mmoles) β-cyclodextrin-EGDMA) complex was dissolved in 5 ml N, N dimethyl formamide in a test tube. To this 10 mg azobisisobutyronitrile was added and the tube was purged with nitrogen for 15 minutes. Polymerization was carried out at 65° C. for 18 hours. After cooling, the DMF solution was added to 200 ml cold water with stirring. The polymer was isolated by raising the temperature to 40° C. The yield of the polymer was 74%. The polymer was characterized by IR and 1H NMR spectroscopy 1H NMR (D2O): 0.9-1.2 δ, (—CH—CH2)—, 2.93 δ, —CH3, 3.5 δ, m, —CH, 4.03 δ, EDA protons, 6.2 δ —NH.
- This example provides the preparation of p(hydroxyethyl methacrylate (HEMA)-co-ethylene glycol dimethacrylate)
- 2 g HEMA (0.015 moles), 2.05 g (1.54 mmoles) (β-cyclodextrin-ethylene glycol dimethacrylate complex was dissolved in 20 ml N, N dimethyl formamide. To is 25 mg azobisisobutyronitrile was added and the test tube was purged with nitrogen for 15 minutes. Polymerization was carried out at 65° C. for 20 hours. The polymer was isolated by precipitation in cold water. The yield of the polymer was 85%. The polymer was characterized by IR and 1H NMR spectroscopy. 1H NMR (CDCl3): 2.0 δ, s, —CH3 of HEMA and EDA, 4.02 δ, d, —CH2 of EDA 4.2 δ, b, —CH2 of HEMA 5.4, 6.02 δ ═CH2.
- This example provides the preparation of p(cetyl acrylate-co-ethylene glycol dimethacrylateCetyl acrylate)
- 0.5 g (1.6 mmoles), 0.427 g (0.32 mmoles) (β-cyclodextrin-ethylene glycol dimethacrylate complex was dissolved in 10 ml N, N dimethyl formamide, 7 mg azobisisobutynitrile was added and nitrogen was bubbled through the solution for 15 minutes. Polymerization was carried out 65° C. for 24 hours. The DMF solution was poured in 50 ml methanol to precipitate (β-cyclodextrin. The polymer was soluble in methanol. It was recovered by evaporation of methanol. The yield of the polymer was 50%. The polymer was characterized by IR and 1H NMR spectroscopy. 1H NMR (CDCl3) 0.9-1.5 δ, cetyl methylene groups, 2.5-3.3 δ, cetyl chain protons, 5.26 δ, ═CH2, 4.03 δ, —CH2 of EDA.
- This example provides the preparation of p(styrene-co-divinyl benzene).
- 1 g styrene (9.6 mmoles) and 0.67 g (0.48 mmoles), β-cyclodextrin-divinyl benzene complex 1:1) was dissolved in 5 ml N, N dimethyl formamide and 10 mg azobisisobutyronitrile was added. Nitrogen was bubbled through the test tube for 15 minutes. Polymerization was carried out at 65° C. for 18 hours. The polymer was isolated adding the DMF solution to 50 ml tetrahydrofuran to remove β-cyclodextrin and the polymer was re-precipitated from tetrahydrofuran. The yield was 55%. The molecular weight of the polymer as characterized by GPC was, Mw=1 1,770, Mn=4170 and polydispersity was 2.82. The polymer was characterized by 1H NMR and IR spectroscopy. 1H NMR (DMSOD6): 7.4 δ, 7.37 δ, 7.29 δ aromatic protons, 6.7 δ ═CH of DVB, 5.9, 5.8 δ, CH.IR (nujol) 698 cm−1, 721 cm−1, 844 cm−1 mono and di substituted aromatic rings, 1597 cm−1, 1658 cm−1 C═C.
- The Advantages of the present invention are:
-
- 1. A simple and easy method of preparation of preparation of copolymers having multiple unsaturations.
- 2. Such polymers can be converted into different forms like thin films, monolayers, micro or nanoparticles and then can be crosslinked in a step to obtain tailor made polymers for wide range of applications.
- 3. Provides a simple method for the preparation for making graft, block or polymers with other morphologies.
Claims (25)
1. A soluble copolymer of vinyl monomers having multiple unsaturation and having the general formula [(Ax) (By)]n, wherein A and B are vinyl monomers that are insoluble in organic solvent and A is vinyl monomer comprising single unsaturation, B is vinyl monomer containing multiple unsaturation and x, y and n are integral values greater than zero.
2. The soluble copolymer as claimed in claim 1 , wherein the vinyl monomer comprising single unsaturation is selected from the group consisting of acrylates, methacrylates, acrylamides comprising of methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyl propyl methacrylate, 2-amino ethyl acrylate hydrochloride butyl acrylate cetyl acrylate, cetyl methacrylate, phenol methacrylate, N-isopropyl acrylamide, acrylamide, N-t-butyl acrylamide, styrene and styrene sulfonic acid.
3. The soluble copolymers as claimed in claim 1 , wherein the vinyl monomer with multiple unsaturations is selected from the group consisting of diacrylates, dimethacrylates, tri or tetra acrylates or methacrylates comprising ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate or aromatic divinyl compounds.
4. The soluble copolymer as claimed in claim 1 , wherein the aromatic divinyl compound is divinyl benzene.
5. The polymer composition as claimed in claim 1 , wherein the content of the monomer with multiple unsaturation in the copolymer may be varied from 0.01-99.9%.
6. A process for the preparation of soluble copolymers of vinyl monomers having general formula [(Ax)(By)]n, wherein A is vinyl monomer comprising one unsaturation, B is vinyl monomer containing multiple unsaturation and x, y and n are integral values greater than zero, the said process comprising the steps of:
a. dissolving an inclusion complex of a monomer, containing multiple unsaturation with a cyclic macromolecular compound in a solvent;
b. adding a vinyl monomer having single unsaturation and a free radical initiator to the reaction mixture of step (a) and polymerizing the solution thus formed to obtain the soluble copolymer.
7. A process as claimed in claim 6 , wherein the inclusion complex of the monomer containing multiple unsaturation is obtained by:
(a) dissolving β-cyclodextrin in water;
(b) adding ethylene glycol dimethacrylate to the reaction mixture of (a) and stirring the same to form a precipitate;
(c) filtering the precipitate and washing the same with water and methanol, and
(d) drying the washed precipitate to obtain the inclusion complex.
8. A process as claimed in claim 6 , wherein the vinyl monomer with single unsaturation is selected from the group consisting of acrylates, methacrylates, acrylamides comprising of methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyl propyl methacrylate, 2-amino ethyl acrylate hydrochloride butyl acrylate cetyl acrylate, cetyl methacrylate, phenol methacrylate, N-isopropyl acrylamide, acrylamide, N-t-butyl acrylamide, styrene and styrene sulfonic acid.
9. A process as claimed in claim 6 , wherein the vinyl monomer with multiple unsaturation is selected from the group consisting of diacrylates, dimethacrylates, tri or tetra acrylates or methacrylates comprising ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, glycerol dimethacrylate, glycerol diacrylate, vinyl methacrylate, vinyl acrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate or aromatic divinyl compounds.
10. A process as claimed in claim 6 , wherein the aromatic divinyl compound is divinyl benzene.
11. A process as claimed in claim 6 wherein in step (a), the solvent used is polar aprotic solvent.
12. A process as claimed in claim 11 , wherein the polar aprotic solvent used is selected from the group comprising of N, N dimethyl formamide, N, N dimethyl acetamide, dimethyl sulfoxide and water.
13. A process as claimed in claim 6 wherein in step (a), the free radical initiator used is a thermal initiator or a photosensitive initiator.
14. A process as claimed in claim 13 , wherein the thermal initiator is selected from the group comprising of azo initiators, peroxide type initiators and redox type initiators.
15. A process as claimed in claim 14 , wherein the azo initiator use is azobisobutyronitrile.
16. A process as claimed in claim 14 , wherein the peroxide initiator used is selected from benzoylperoxide and t-butyl hydroperoxide.
17. A process as claimed in claim 14 , wherein the redox initiator used is potassium persulphate and ammonium persulphate.
18. A process as claimed in claim 13 , wherein the photosensitive initiator is selected from the group comprising of cumene hydroperoxide, benzoin ethyl ether, 2,2-dimethoxy-2-phenyl acetophenone, 1-hydroxy cyclohexyl-1-phenyl ketone (Irgacure-184), bis(2,4,6-trimethyl benzoyl)phenyl phosphine (Irgacure-819).
19. A process of preparation of a crosslinked polymer from the soluble copolymers of claim 1 , the said process comprising the steps of:
a. dissolving soluble copolymer of claim 1 in a solvent along with a free radical initiator, and
b. heating or irradiating the mixture of step (a) to obtain the cross linked polymer.
20. A process as claimed in claim 19 , wherein in step (a) the free radical initiator used is a thermal initiator or a photo initiator.
21. A process as claimed in claim 19 , wherein the thermal initiator is selected from the group comprising of azo initiators and peroxide type initiators.
22. A process as claimed in claim 21 , wherein the azo initiator used is azobisbutyronitrile.
23. A process as claimed in claim 21 , wherein the peroxide initiator used is selected from benzoylperoxide and t-butyl hydroperoxide.
24. A process as claimed in claim 19 , wherein the photo initiator is selected from the group comprising of cumene hydroperoxide, benzoin ethyl ether, 2,2-diethoxy-2-phenyl acetophenone, 1-hydroxy cyclohexyl-1-phenyl ketone (Irgacure-184), bis(2,4,6-trimethyl benzoyl)phenyl phosphine.
25. A process as claimed in claim 19 wherein in step (b), the reaction mixture is heated upto temperature in the range of 40 to 80° C. under inert atmosphere to obtain the cross-linked polymer.
Priority Applications (2)
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US10/700,511 US20050096443A1 (en) | 2003-11-05 | 2003-11-05 | Soluble polymers comprising unsaturation and process for preparation thereof |
US12/257,996 US7763688B2 (en) | 2003-11-05 | 2008-10-24 | Soluble polymers comprising unsaturation and process for preparation thereof |
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US10/700,511 US20050096443A1 (en) | 2003-11-05 | 2003-11-05 | Soluble polymers comprising unsaturation and process for preparation thereof |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050196343A1 (en) * | 2004-02-27 | 2005-09-08 | Molecular Therapeutics, Inc. | Degradable nanoparticles |
US20060094844A1 (en) * | 2004-10-29 | 2006-05-04 | Council Of Scientific And Industrial Research | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
US20070265365A1 (en) * | 2004-10-29 | 2007-11-15 | Patil Prerana M | Water Soluble Polymers Containing Vinyl Unsaturation, Their Crosslinking and Process for Preparation Thereof |
US7560522B2 (en) * | 2004-06-28 | 2009-07-14 | Council Of Scientific And Industrial Research | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
US20150073091A1 (en) * | 2012-04-27 | 2015-03-12 | Osaka University | Gel with self-restorability and shape-memory property and process for producing same |
CN117700602A (en) * | 2023-03-22 | 2024-03-15 | 广东吉美帮新材料有限公司 | Quick-drying high-molecular emulsion with strong wet adhesion and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645810A (en) * | 1984-08-23 | 1987-02-24 | Usm Corporation | Adhesive bonding |
US4897215A (en) * | 1987-05-16 | 1990-01-30 | Basf Aktiegesellschaft | Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds |
US5756559A (en) * | 1992-02-06 | 1998-05-26 | Dentsply Research & Development | Method and composition for adhering to tooth structure |
US6646068B2 (en) * | 1998-03-12 | 2003-11-11 | Lucite International Uk Limited | Polymer composition |
US6691715B2 (en) * | 1999-07-16 | 2004-02-17 | Calgon Corporation | Water soluble polymer composition and method of use |
US6727320B2 (en) * | 1998-11-02 | 2004-04-27 | Henkel Loctite Corporation | Polymerizable compositions in non-flowable forms |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4906488A (en) * | 1987-05-01 | 1990-03-06 | Arcade, Inc. | Modification of permeant |
JPH03259083A (en) * | 1990-03-09 | 1991-11-19 | Oji Kako Kk | Immobilization of biocatalyst |
US5258414A (en) * | 1990-05-04 | 1993-11-02 | American Maize Technology, Inc. | Adhesives and sealants |
IT1255981B (en) * | 1991-04-30 | 1995-11-17 | Ministero Dell Uni E Della | MULTI-COMPONENT ADHESIVE COMPOSITION |
US5521266A (en) * | 1994-10-28 | 1996-05-28 | Rohm And Haas Company | Method for forming polymers |
US5792821A (en) * | 1997-01-06 | 1998-08-11 | American Dental Association Health Foundation | Polymerizable cyclodextrin derivatives |
US6229062B1 (en) * | 1999-04-29 | 2001-05-08 | Basf Aktiengesellschaft Corporation | Superabsorbent polymer containing odor controlling compounds and methods of making the same |
DE19963586A1 (en) * | 1999-12-29 | 2001-07-12 | Dupont Performance Coatings | Process for the preparation of lacquer binders and their use in coating compositions |
-
2003
- 2003-11-05 US US10/700,511 patent/US20050096443A1/en not_active Abandoned
-
2008
- 2008-10-24 US US12/257,996 patent/US7763688B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645810A (en) * | 1984-08-23 | 1987-02-24 | Usm Corporation | Adhesive bonding |
US4897215A (en) * | 1987-05-16 | 1990-01-30 | Basf Aktiegesellschaft | Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds |
US5756559A (en) * | 1992-02-06 | 1998-05-26 | Dentsply Research & Development | Method and composition for adhering to tooth structure |
US6646068B2 (en) * | 1998-03-12 | 2003-11-11 | Lucite International Uk Limited | Polymer composition |
US6727320B2 (en) * | 1998-11-02 | 2004-04-27 | Henkel Loctite Corporation | Polymerizable compositions in non-flowable forms |
US6691715B2 (en) * | 1999-07-16 | 2004-02-17 | Calgon Corporation | Water soluble polymer composition and method of use |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050196343A1 (en) * | 2004-02-27 | 2005-09-08 | Molecular Therapeutics, Inc. | Degradable nanoparticles |
US20070213486A1 (en) * | 2004-06-28 | 2007-09-13 | Patil Prerana M | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
US7560522B2 (en) * | 2004-06-28 | 2009-07-14 | Council Of Scientific And Industrial Research | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
US20060094844A1 (en) * | 2004-10-29 | 2006-05-04 | Council Of Scientific And Industrial Research | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
US20070265365A1 (en) * | 2004-10-29 | 2007-11-15 | Patil Prerana M | Water Soluble Polymers Containing Vinyl Unsaturation, Their Crosslinking and Process for Preparation Thereof |
US20150073091A1 (en) * | 2012-04-27 | 2015-03-12 | Osaka University | Gel with self-restorability and shape-memory property and process for producing same |
US10106628B2 (en) * | 2012-04-27 | 2018-10-23 | Osaka University | Gel with self-restorability and shape-memory property and process for producing same |
US20190092880A1 (en) * | 2012-04-27 | 2019-03-28 | Osaka University | Gel with self-restorability and shape-memory property and process for producing same |
CN117700602A (en) * | 2023-03-22 | 2024-03-15 | 广东吉美帮新材料有限公司 | Quick-drying high-molecular emulsion with strong wet adhesion and preparation method thereof |
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US20090076181A1 (en) | 2009-03-19 |
US7763688B2 (en) | 2010-07-27 |
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