WO2009063211A1 - Methods of encapsulating a substance - Google Patents
Methods of encapsulating a substance Download PDFInfo
- Publication number
- WO2009063211A1 WO2009063211A1 PCT/GB2008/003838 GB2008003838W WO2009063211A1 WO 2009063211 A1 WO2009063211 A1 WO 2009063211A1 GB 2008003838 W GB2008003838 W GB 2008003838W WO 2009063211 A1 WO2009063211 A1 WO 2009063211A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- group
- substance
- formula
- optionally substituted
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000000126 substance Substances 0.000 title claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 239000002775 capsule Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- -1 halide ion Chemical class 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000383 hazardous chemical Substances 0.000 claims description 4
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 229940063013 borate ion Drugs 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 claims description 2
- 229940075931 sodium dithionate Drugs 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 abstract 3
- 229920000642 polymer Polymers 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 239000008188 pellet Substances 0.000 description 19
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910003827 NRaRb Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FYIUUXMLPZZJSU-UHFFFAOYSA-N n,n,n',n'-tetrakis(prop-2-enyl)decane-1,10-diamine Chemical compound C=CCN(CC=C)CCCCCCCCCCN(CC=C)CC=C FYIUUXMLPZZJSU-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- QRWAIZJYJNLOPG-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)C(=O)C1=CC=CC=C1 QRWAIZJYJNLOPG-UHFFFAOYSA-N 0.000 description 1
- MZAGXDHQGXUDDX-JSRXJHBZSA-N (e,2z)-4-ethyl-2-hydroxyimino-5-nitrohex-3-enamide Chemical compound [O-][N+](=O)C(C)C(/CC)=C/C(=N/O)/C(N)=O MZAGXDHQGXUDDX-JSRXJHBZSA-N 0.000 description 1
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical compound BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 description 1
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 description 1
- RRQGZMDHLIAOLY-UHFFFAOYSA-N 1-bromopiperidine Chemical compound BrN1CCCCC1 RRQGZMDHLIAOLY-UHFFFAOYSA-N 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical class ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical class COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 description 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 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- GGMYKFODAVNSDF-UHFFFAOYSA-N o-phenyl phenylsulfanylmethanethioate Chemical compound C=1C=CC=CC=1SC(=S)OC1=CC=CC=C1 GGMYKFODAVNSDF-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- YYWLHHUMIIIZDH-UHFFFAOYSA-N s-benzoylsulfanyl benzenecarbothioate Chemical class C=1C=CC=CC=1C(=O)SSC(=O)C1=CC=CC=C1 YYWLHHUMIIIZDH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- 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
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F26/04—Diallylamine
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Definitions
- This invention relates to methods of encapsulating a substance.
- Microencapsulation is a well known process by which small amounts of a gas, liquid or solid are encapsulated within a shell material in order to shield the encapsulated substance.
- the contents of the capsule can be released at a later time by various means that are well known in the art, such as mechanical rupture of the capsule wall, or melting of the capsule wall.
- the individual capsules are of small dimensions, and contain only a small amount of the substance.
- the microencapsulation process involves the mixing of immiscible liquid phases, i.e. a polar phase and a non-polar phase, in order for microencapsulation to be brought about. Most activity has been directed towards encapsulation of non-polar materials, although the Applicant's earlier International patent application WO 2007/012860 describes a system which can readily permit encapsulation of polar substances, in particular water.
- the present inventors have realised that there is a need for a technique which can provide larger capsules which encapsulate larger amounts of a desired substance. Furthermore, the present inventors have realised that it would be desirable to be able to readily produce the capsules in a desired size and/or shape. This is not readily possible, if at all, with conventional microencapsulation techniques, in which the size of the micro capsules produced is essentially determined by the physico-chemical nature of the microencapsulation system utilised. Furthermore, the present inventors have realised that it would be desirable and convenient to be able to perform encapsulation without requiring the presence of a two-phase polar/non-polar system.
- the present invention in at least some of its embodiments, addresses the above described problems and desires.
- a method of encapsulating a substance including the steps of: providing a monomer which includes a group of sub-formula (I)
- R 2 and R 3 are independently selected from (CR 7 R 8 ) n , or a group CR 9 R 10 ,
- R 7 and R 8 are independently selected from hydrogen, halo or hydrocarbyl, and either one of R 9 or R 10 is hydrogen and the other is an electron withdrawing group, or R 9 and R 10 together form an electron withdrawing group, and R 4 and R 5 are independently selected from CH or CR 11 where R 11 is an electron withdrawing group;
- the dotted lines indicate the presence or absence of a bond
- X 1 is a group CX 2 X 3 where the dotted line bond to which it is attached is absent and a group CX 2 where the dotted line bond to which it is attached is present
- Y 1 is a group CY 2 Y 3 where the dotted line bond to which it is attached is absent and a group
- CY 2 where the dotted line bond to which it is attached is present, and X 2 , X 3 , Y 2 and Y 3 are independently selected from hydrogen, fluorine or other substituents; R 1 is selected from hydrogen, halo, nitro, or hydrocarbyl, optionally substituted or interposed with functional groups;
- R 12 is selected from hydrogen, halo, nitro, hydrocarbyl, optionally D 3 D 5 V 1 substituted or interposed with functional groups, or 1 ⁇ - — ⁇ ; and Z is an anion of charge m; mixing the monomer with the substance and, optionally, at least one of a solvent for the monomer and an initiator to form a monomer containing mixture; placing a pre-determined quantity of the monomer containing mixture in a pre-determined location so as to form a desired shape; and polymerising the monomer so as to produce a polymeric matrix of a desired shape which encapsulates the substance.
- a solvent for the monomer when used, acts to dissolve the monomer, and is particularly useful when the monomer is not a liquid and the substance to be encapsulated is not capable of dissolving the monomer.
- the pre-determined quantity of the monomer containing mixture is placed in a mould of a desired shape. Subsequent polymerisation of the monomer produces a polymeric matrix of a shape essentially corresponding to that of the mould.
- one or more pre-determined quantities of the monomer containing mixture are deposited in a controlled and repeatable manner on one or more surfaces having controlled characteristics so that the quantities of the monomer containing mixtures form desired shapes, and the monomer in each deposited mixture is polymerised to produce at least one polymeric matrix of a desired shape, each of which encapsulates the substance.
- a pre-determined quantity of the monomer containing mixture may be deposited and optionally spread over a surface so as to enable the production of a film of the polymeric matrix.
- a plurality of pre-determined quantities of the monomer contained mixture may be deposited separately at discrete locations on a surface, enabling the production of a plurality of polymeric matrices of a desired shape.
- the surface or surfaces may comprise a glass substrate optionally with a surface treatment such as a silane treatment.
- the polymeric matrix may be subjected to a heat treatment.
- the polymeric matrix may be a capsule of dimensions greater than 1mm.
- the substance is a liquid.
- the liquid may act as a solvent for the monomer, and the mixing of the monomer with the liquid causes the liquid to dissolve the monomer.
- the substance in embodiments in which the substance is a liquid, the substance may be a pure liquid, or the liquid may include one or more solutes dissolved in a solvent. In the latter instance, the substance may be an acid, such as nitric acid, phosphoric acid or citric acid. In embodiments in which the substance is an acid, it is preferred that R 1 and R 12 are not hydrogen so that the monomer and polymer are substantially neutral.
- the substance includes a polar liquid.
- the monomer and the substance may be additionally mixed with a solvent for the monomer, wherein the solvent for the monomer is a polar liquid.
- the polar liquid is water, although other polar liquids, such as dimethyl sulphoxide (DMSO) might be used.
- the substance is a solid.
- the substance may be an ionic solid, such as sodium dithionate.
- it can be particularly useful to utilise at least one solvent for the monomer when mixing the monomer with the substance to form a monomer containing mixture, particularly when the monomer is a solid as well.
- the invention can be used to encapsulate a wide range of substances.
- An advantage of the invention is that it can be used to encapsulate hazardous substances, allowing a hazardous substance to be transported in a safe manner.
- a substance may be a hazardous chemical, such as a biocide, an oxidising agent, a reducing agent, an acid, or an alkali.
- the substance can be released from the polymeric matrix by at least partially dissolving the polymer.
- the polymer may be dissolved by contact with a polar liquid, and preferably the polar liquid is water. It is advantageous that it is readily possible to produce polymers from monomers which include a group of sub-formula (I) which can be dissolved by water.
- the monomer is polymerised by exposure to ultraviolet radiation.
- Alternative polymerisation methods include the application of heat (which may be. in the form of IR radiation), where necessary in the presence of an initiator, by the application of other sorts of initiator such as chemical initiators, or by initiation using an electron beam.
- chemical initiator refers to compounds which can initiate polymerisation such as free radical initiators and ion initiators such as cationic or anionic initiators as are understood in the art.
- polymerisation may take place either spontaneously or in the presence of a suitable initiator.
- Suitable initiators include 2, 2' - azobisisobutyronitrile (AIBN), aromatic ketones such as benzophenones in particular acetophenone; chlorinated acetophenones such as di- or , tri-chloracetophenone; dialkoxyacetophenones such as dimethoxyacetophenones (sold under the trade name "Irgacure 651”) dialkyihydroxyacetophenones such as dimethylhydroxyacetophenone (sold under the trade name "Darocure 1173"); substituted dialkylhydroxyacetophenone alkyl ethers such compounds of formula
- R y is alkyl and in particular 2, 2-dimethylethyl
- R x is hydroxyl or halogen such as chloro
- R p and R q are independently selected from alkyl or halogen such as chloro
- alkyl or halogen such as chloro
- i-benzoylcyclohexanol-2 sold under the trade name "Irgacure 184"
- benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers in particular benzoin butyl ether, dialkoxybenzoins such as dimethoxybenzoin or deoxybenzoin
- dibenzyl ketone acyloxime esters such as methyl or ethyl esters of acyloxime (sold under the trade name "Quantaqure PDO”); acylphosphine oxides, acylphosphonates
- R z is alkyl and Ar is an aryl group; dibenzoyl disulphides such as 4, 4'- dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone; 4, 4'-bis (N, N-dialkyamino) benzophenone; fluorenone; thioxanthone; benzil; or a compound of formula where Ar is an aryl group such as phenyl and R z is alkyl such as methyl (sold under the trade name "Speedcure BMDS").
- dibenzoyl disulphides such as 4, 4'- dialkylbenzoyldisulphide
- diphenyldithiocarbonate benzophenone
- fluorenone thioxanthone
- benzil or a compound of formula where Ar is an aryl group such as phenyl and R z is alkyl
- alkyl refers to straight or branched chain alkyl groups, suitably containing up to 20 and preferably up to 6 carbon atoms.
- alkenyl and alkynyl refer to unsaturated straight or branched chains which include for example from 2-20 carbon atoms, for example from 2 to 6 carbon atoms. Chains may include one or more double to triple bonds respectively.
- aryl refers to aromatic groups such as phenyl or naphthyl.
- hydrocarbyl refers to any structure comprising carbon and hydrogen atoms.
- these may be alkyl, alkenyl, alkynyl, aryl such as phenyl or napthyl, arylalkyl, cycloalkyl, cycloalkenyl or cycloalkynyl.
- aryl such as phenyl or napthyl
- arylalkyl cycloalkyl
- cycloalkenyl or cycloalkynyl Suitably they will contain up to 20 and preferably up to 10 carbon atoms.
- heteroatom such as oxygen, sulphur or nitrogen.
- Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.
- t is 0 or an integer of 1-3.
- heteroatom refers to non-carbon atoms such as oxygen, nitrogen or sulphur atoms. Where the nitrogen atoms are present, they will generally be present as part of an amino residue so that they will be substituted for example by hydrogen or alkyl.
- amide is generally understood to refer to a group of formula
- R a and R b are hydrogen or an optionally substituted hydrocarbyl group.
- sulphonamide will refer to a group of formula S(O) 2 NR a R b .
- Suitable groups R a include hydrogen or methyl, in particular hydrogen.
- the nature of any electron withdrawing group or groups additional to the amine moiety used in any particular case will depend upon its position in relation to the double bond it is required to activate, as well as the nature of any other functional groups within the compound.
- electron withdrawing group includes within its scope atomic substituents such as halo, e.g. fluro, chloro and bromo, and also molecular substituents such as nitrile, trifluoromethyl, acyl such as acetyl, nitro, or carbonyl.
- R 11 is an electron withdrawing group, it is suitably acyl such as acetyl, nitrile or nitro.
- R 7 and R 8 are independently selected from fluoro, chloro or alky! or H. In the case of alkyl, methyl is most preferred.
- X 2 , X 3 , Y 2 and Y 3 are all hydrogen.
- At least one, and possibly all, of X 2 , X 3 , Y 2 and Y 3 is a substituent other than hydrogen or fluorine, in which instance it is preferred that at least one, and possibly all, of X 2 , X 3 , Y 2 and Y 3 is an optionally substituted hydrocarbyl group.
- Particularly preferred examples are Ci to C 4 alkyl groups, especially methyl or ethyl.
- X 2 , X 3 , Y 2 and Y 3 are aryl and/or heterocyclic such as pyridyl, pyrimidinyl, or a pyridine or pyrimidine containing group.
- X 1 and Y 1 are groups CX 2 X 3 and CY 1 Y 2 respectively and the dotted lines represent an absence of a bond.
- preferred compounds are those of sub-formula (IA)
- Preferred anions Z m" are halide ions, preferably Br ' , tosylate, triflate, a borate ion, PFs " , or a carboxylic acid ester anion.
- a preferred group of the compounds for use in the method of the invention is a compound of structure (II)
- X 1 , X 2 , X 3 , Y 1 , Y 2 , Y 3 , R 2 , R 3 , R 4 , R 5 and the dotted bonds are as defined in relation to formula (I) above, r is an integer of 1 or more, and R 6 is a bridging group, an optionally substituted hydrocarbyl group, a perhaloalkyl group, a siloxane group or an amide.
- R 6 is an optionally substituted hydrocarbyi group, a perhaloalkyl group, a siloxane group or an amide.
- networks are formed whose properties maybe selected depending upon the precise nature of the R 6 group, the amount of chain terminator present and the polymerisation conditions employed.
- Examples of bridging groups can be found in WO 00/06610.
- R 6 or R 6' may be an optionally substituted hydrocarbyi group having three or more carbon atoms.
- R 6 or R 6' may be a straight or branched chain alkyl group, optionally substituted or interposed with functional groups.
- R 6 or R 6 may have between one and twenty carbon atoms, preferably between two and twelve carbon atoms.
- the term 'between x and y carbon atoms' as used herein refers to the range x to y carbon atoms and includes embodiments having x carbon atoms and embodiments having y carbon atoms.
- R 1 and R 6 or R 6' together with the quatemarised N atom to which they are attached form a heterocyclic structure.
- R 1 and R 6 or R 6 together with the quaternerised N to which they are attached form an optionally substituted heterocyclic structure comprising a four to eight membered ring.
- the optionally substituted heterocyclic structure may be a five or a six membered ring.
- R 6 or R 6 together with the quatemarised N to which they are attached form an optionally substituted piperidine ring.
- Polymeric matrices formed from these monomers are particularly useful for encapsulating acids, because they can be stable over time.
- the monomer may be a compound of formula (IV)
- the heterocyclic structure may include at least one additional heteroatom in addition to the quaternarised N to which R 1 and R 6 or R 6' are attached.
- the additional heteroatom may be N, O or S.
- the heterocyclic structure includes at least two N heteroatoms, in which instance the monomer may be a compound of formula (V)
- A is a four to eight membered heterocyclic ring and the quaternarised nitrogens are present at any suitable pair of positions in the ring.
- A is a five or six membered heterocyclic ring.
- the ring may be a 1 ,2, a 1 ,3, or a
- A is an optionally substituted piperazine ring.
- the monomer may be a compound of formula (Vl)
- the monomer is a compound of formula
- R 13 is a straight or branched alkyl group, preferably having between one and twenty carbon atoms, most preferably having between two and twelve carbon atoms;
- R 14 is hydrogen or a straight or branched alkyl group, preferably having between one and five carbon atoms, most preferably methyl or ethyl.
- the monomer is a compound of formula (VIII)
- the monomer is a compound of formula (IX)
- R 14 is methyl
- Z m" is Br ' .
- This anion is particularly useful when acids such as nitric acid are encapsulated, since it can confer stability on the resulting polymer.
- Tosylate and triflate anions are also stable iri acidic media and thus represent further preferred embodiments of Z m' when acids are encapsulated.
- R 1 may be H, an alkyl group, preferably having less than 3 carbon atoms,
- R 15 and R 16 are independently selected from (CR 7 R 8 ) n , or a group CR 9 R 10 , CR 7 R 8 CR 9 R 10 or CR 9 R 10 CR 7 R 8 where n is 0, 1 or 2, R 7 and R 8 are independently selected from hydrogen, halo or hydrocarbyl, and either one of R 9 or R 10 is hydrogen and the other is an electron withdrawing group, or R 9 and R- 10 together form an electron withdrawing group, the dotted lines indicate the presence or absence of a bond, and Z 1 is a group CZ 2 Z 3 where the dotted line bond to which it is attached is absent and a 'group CZ 2 where the dotted line bond to which it is attached is present, and Z 2 ,Z 3 are independently selected from hydrogen, fluorine or other substituents.
- the monomer is preferably of the following formula
- R 6 is as previously defined and may be a group R 6' as previously defined.
- the step of polymerising the monomer may produce a homopolymer.
- the step of polymerising the monomer may produce a copolymer, the monomer being mixed with different monomeric units.
- the co- monomer having different monomeric units may include a group of sub-formula (I).
- the co-monomer may be according to any of the formulae described above.
- the co-monomer may be of a different class of compounds.
- the monomer may be copolymerised with a cross-linker.
- the cross-linker may be a compound of formula (VII) as described above and preferably is a compound of formula (VIII) or (IX) as defined above.
- the substance encapsulated within a polymeric matrix formed from a copolymer is released by at least partially dissolving the copolymer.
- the copolymer can be wholly dissolved, or portions of the polymeric matrix may be dissolved to release the substance. In the latter instance, it is envisaged that the polymeric matrix may retain enough structural integrity so that it can be removed, from the point of release after sufficient time has elapsed so that a desired quantity of the substance has been released.
- the extent to which the polymeric matrix dissolves during release of the substance can be varied for example by varying the concentration of cross-linker utilised in the preparation of the monomer containing mixture.
- At least some monomers in which R 1 and R 6 or R 6 together with the quatemarised N atom to which they are attached form a heterocyclic structure are believed to be novel perse, as are polymers formed therefrom. Accordingly, in further aspects of the invention there are provided compounds of the type described above in which R 1 and R 6 or R 6 together with the quatemarised N atom to which they are attached form a heterocyclic structure, and polymers formed therefrom. Yet further aspects of the invention provide methods of making said compounds and methods of polymerising said polymers. The methods utilised can be as generally described herein, although the skilled reader will appreciate that in these aspects of the invention the polymerisation is not necessarily in connection with a method of encapsulating a substance.
- the polymerisation can refer to a general polymerisation step, e.g. one in which a polymer is produced without the presence of a substance which is encapsulated within the polymer.
- a general polymerisation step e.g. one in which a polymer is produced without the presence of a substance which is encapsulated within the polymer.
- Figure 1 is a schematic diagram illustrating (a) a first method, (b) a second method and (c) a third method of the invention
- Figure 2 shows pH change after addition of sodium dithionite containing film
- Figure 3 shows pH change after addition of nitric acid containing pellets.
- Figure 1 shows three embodiments of methods of the present invention. In all three cases, a monomer containing mixture 10 is prepared using techniques which are further explained herein.
- a known quantity of the monomer containing mixture 10 is deposited on a surface 12 and spread with a spreader 14 to form a thin film 16.
- predetermined quantities of the monomer containing mixture 10 are deposited on to the surface 12 to form discrete droplets 17 which remain in place, i.e. no spreading is performed.
- monomer containing mixture 10 is introduced into a mould 18.
- Diallylamine (99%, Aldrich, 65g) was added to a mixture of 1 ,5- dibromopetane (97%, Aldrich, 15Og), potassium carbonate (99%, 18Og) and ethyl alcohol (99+%, 100ml) into a 3 necked, 1 litre reaction flask with temperature monitoring and reflux. After heating towards reflux the reaction proceeded far more quickly from 70 0 C onwards. The reaction was maintained at reflux for 1 hour and then cooled to room temperature and left for 18 hours.
- the monomer formulation was made by dissolving monomer X (2.0 g) into water (0.5Og from tap, pH ⁇ 7.6) followed by addition of Ciba lrgacure 184 photoinitiator (2% w/w CPQ) with thorough dissolving and mixing. Finely powered sodium dithionite (0.6Og) was then added and mixed thoroughly into the solution.
- a thin film (approximately 1mm thickness) was then made by the spreading the monomer formulation with a hand K-bar spreader onto a glass substrate. This was cured under a focused Fe doped Hg lamp (FusionUV F300S, 120W/cm) at 2m/min with 3 passes.
- FusionUV F300S, 120W/cm focused Fe doped Hg lamp
- a monomer formulation was made by dissolving monomer 1 (2.5 g) into dilute nitric acid (0.87 g of 35wt% in water) followed by addition of Ciba Irgacure 2022 photoinitiator (3% w/w with respect to the monomer) with thorough dissolving and mixing.
- the solution was then transferred to a needle syringe and deposited as small droplets, 2 to 3mm in diameter, onto a 'non-stick 1 silane (Repelcote (VS), BDH) treated glass plate.
- the droplets were cured using a Ga doped Hg bulb (120W/cm, Fusion UV300S) by passing the plate twice under the lamp at 1.5 m/min for the top and twice for underside of the glass.
- Solid pellets were formed, which were then dried further by placing in an oven for 60 minutes at 7O 0 C. This drying step removed ⁇ 20% by weight of the water in the pellets. The dried pellets were then removed from the glass by gently scraping off the glass surface. A portion of these (0.714g) were placed into a smaller beaker containing 50ml of tap water at 2O 0 C with constant stirring with the pH monitored overtime using a pH meter. As a control experiment, the same amount of nitric acid that was added to the pellets was monitored for pH vs time under the same conditions.
- Diallylamine (99%, 7Og, 0.72moles), 1 ,10-dibromodecane (97%, 10Og, 0.33moles) and potassium carbonate (99%+ dry, 20Og, 0.69moles) were charged into a reaction vessel containing ethanol (100ml) and refiuxed for 96 hours. After cooling the reaction mixture, dichloromethane (50ml) was added and the mixture was then filtered to remove the potassium carbonate and other salts. Solvent and excess diallylamine were removed by rotary evaporation to produce yellow oil, which was purified by column chromatography using siiica (60 A) and dichloromethane as eluent. Dichloromethane was removed under vacuum to produce the N,N,N',N'-tetraallyldecane-1 ,10-diamine intermediate as a pale yellow oil. Yield ⁇ 75%.
- N,N,N',N'-tetraallyldecane 1,10 diamine intermediate (33.26g, lOOmmoles) was added to dichloromethane (dried, 23Og, 2.7moles) and charged into a reaction flask and was heated to reflux.
- Methyl trifluoromethane sulphonate (>98%, .
- the solution was transferred to a syringe and added as drops onto a hydrophobic silicone treated glass plate (Repelcote (VS) BDH); each drop ranged from approximately 1mm to 3mm in diameter.
- the plate was then passed twice under a UV lamp (FusionUVF300S, Ga doped bulb, 120W/cm, 1.5 m/min) and then placed into an oven at 90 0 C for 1 hour, which partially dried the pellets to a rubbery solid.
- the target molecule 3 is shown below
- Methyl-para-toluene sulfonate (98%, 216g, 1.1598 moles) was added dropwise over 120 minutes to a refluxing mixture of the diamine intermediate (12Og, 0.5128 moles) and tetrahydrofuran (60OmI). After a further 120 minutes refluxing, the reaction mixture was allowed to cool and the product precipitated as a soft white, hygroscopic solid. The supernatant liquid (containing THF and any unreacted starting materials) was removed and then approximately 1500ml of acetone was added to the flask. The mixture was then stirred for 15 minutes and the white precipitate was filtered under vacuum (yield approx. 87%). This product was then washed in fresh, cold acetone and dried at ⁇ 4O 0 C to yield a white powder (final yield approx. 65%).
- Example 5 The same method as for Example 5 was used but using following materialsiN.N.N'.N' tetrallylpropane-1 ,3-dimethylammonium tosylate(0.5Og), N 1 N- diallylpiperidine bromide (1.5Og) with Nitric acid (35wt%, 0.7Og) and lrgacure 2022 (3% w/w monomer).
- the polymer was mostly insoluble in water with ⁇ 10% soluble residue produced.
- Acid was released gradually in water (20 0 C) with a lower pH reached more quickly when 60wt% nitric acid was used.
- a similar pH was achieved from the acid containing pellets compared to a reference of the equivalent amount of nitric acid solution in water; the two values becoming more similar by increasing 0 the duration of the pellets in water.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN200880116432A CN101861204A (en) | 2007-11-17 | 2008-11-17 | Methods of encapsulating a substance |
MX2010005200A MX2010005200A (en) | 2007-11-17 | 2008-11-17 | Methods of encapsulating a substance. |
EP08850044A EP2219776A1 (en) | 2007-11-17 | 2008-11-17 | Methods of encapsulating a substance |
JP2010533654A JP2011502778A (en) | 2007-11-17 | 2008-11-17 | Methods for encapsulating substances |
CA2704938A CA2704938A1 (en) | 2007-11-17 | 2008-11-17 | Methods of encapsulating a substance |
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GBGB0722631.9A GB0722631D0 (en) | 2007-11-17 | 2007-11-17 | Method of encapsulating a substance |
GB0722631.9 | 2007-11-17 |
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WO2009063211A1 true WO2009063211A1 (en) | 2009-05-22 |
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US (1) | US20090174100A1 (en) |
EP (1) | EP2219776A1 (en) |
JP (1) | JP2011502778A (en) |
KR (1) | KR20100098397A (en) |
CN (1) | CN101861204A (en) |
CA (1) | CA2704938A1 (en) |
GB (2) | GB0722631D0 (en) |
MX (1) | MX2010005200A (en) |
WO (1) | WO2009063211A1 (en) |
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WO2012017237A1 (en) | 2010-08-02 | 2012-02-09 | Novel Polymer Solutions Limited | Composite articles and methods of producing same |
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JP2016087479A (en) * | 2014-10-29 | 2016-05-23 | 国立大学法人 鹿児島大学 | Method for producing micro-capsules or beads |
CN104447508B (en) * | 2014-12-16 | 2017-02-22 | 湖南科技大学 | Preparation method of bromized N,N-diallyl piperidine onium salt cationic monomer |
EP3365381B1 (en) | 2015-10-21 | 2020-04-22 | Saudi Arabian Oil Company | Cationic polymers and porous materials |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000006610A2 (en) * | 1998-07-25 | 2000-02-10 | The Secretary Of State For Defence | Polymer production |
WO2000006533A2 (en) * | 1998-07-25 | 2000-02-10 | The Secretary Of State For Defence | Monomers and network polymers obtained therefrom |
WO2007012860A1 (en) * | 2005-07-27 | 2007-02-01 | Novel Polymer Solutions Ltd | Methods of forming a barrier |
US20070149694A1 (en) * | 2003-07-03 | 2007-06-28 | Venkataram Krishnan | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
WO2008001102A1 (en) * | 2006-06-30 | 2008-01-03 | Novel Polymer Solutions Limited | Method of producing a polymeric material, polymer, monomeric compound and method of preparing a monomeric compound |
WO2008024509A2 (en) * | 2006-08-24 | 2008-02-28 | Mallard Creek Polymers, Inc. | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
US20080233062A1 (en) * | 2006-08-24 | 2008-09-25 | Venkataram Krishnan | Cationic latex as a carrier for active ingredients and methods for making and using the same |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3912693A (en) * | 1973-04-05 | 1975-10-14 | Nitto Boseki Co Ltd | Process for producing polyamines |
US4121986A (en) * | 1975-05-07 | 1978-10-24 | Ici Australia Limited | Process for the polymerization of polyallylamines in the presence of a mineral acid solution |
US4857406A (en) * | 1987-04-10 | 1989-08-15 | The Mead Corporation | Microcapsules with polysalt capsule walls and their formation |
IE60710B1 (en) * | 1987-08-26 | 1994-08-10 | Rohm & Haas | Process for microencapsulation, uses of polymers prepared by said process, and compositions containing polymers prepared by said process |
US5674481A (en) * | 1993-06-24 | 1997-10-07 | Wahi; Ashok L. | Electrostatically charged nasal topical application product |
JPH08134114A (en) * | 1994-11-07 | 1996-05-28 | Daiso Co Ltd | Method for polymerizing diallyldialkylammonium compound |
GB9816169D0 (en) * | 1998-07-25 | 1998-09-23 | Secr Defence | Adhesives and sealants |
GB9928621D0 (en) * | 1999-12-04 | 2000-02-02 | Secr Defence Brit | Composition for use in stereolithography |
DE10252032B4 (en) * | 2002-11-06 | 2006-04-13 | Teller, Joachim, Dr. | Process for the preparation of spherical particles and spherical particles |
JP4412598B2 (en) * | 2004-07-20 | 2010-02-10 | 第一工業製薬株式会社 | Ionic polymer gel electrolyte and precursor composition thereof |
GB0519045D0 (en) * | 2005-09-17 | 2005-10-26 | Ionic Polymer Solutions Ltd | Conductive polymers |
GB0606016D0 (en) * | 2006-03-25 | 2006-05-03 | Ionic Polymer Solutions Ltd | Quaternary ammonium compounds and their uses |
-
2007
- 2007-11-17 GB GBGB0722631.9A patent/GB0722631D0/en not_active Ceased
-
2008
- 2008-11-17 MX MX2010005200A patent/MX2010005200A/en unknown
- 2008-11-17 KR KR1020107013059A patent/KR20100098397A/en not_active Application Discontinuation
- 2008-11-17 JP JP2010533654A patent/JP2011502778A/en active Pending
- 2008-11-17 EP EP08850044A patent/EP2219776A1/en not_active Withdrawn
- 2008-11-17 WO PCT/GB2008/003838 patent/WO2009063211A1/en active Application Filing
- 2008-11-17 CA CA2704938A patent/CA2704938A1/en not_active Abandoned
- 2008-11-17 GB GB0820937.1A patent/GB2454803B/en not_active Expired - Fee Related
- 2008-11-17 CN CN200880116432A patent/CN101861204A/en active Pending
- 2008-11-17 US US12/271,961 patent/US20090174100A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000006610A2 (en) * | 1998-07-25 | 2000-02-10 | The Secretary Of State For Defence | Polymer production |
WO2000006533A2 (en) * | 1998-07-25 | 2000-02-10 | The Secretary Of State For Defence | Monomers and network polymers obtained therefrom |
US20070149694A1 (en) * | 2003-07-03 | 2007-06-28 | Venkataram Krishnan | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
WO2007012860A1 (en) * | 2005-07-27 | 2007-02-01 | Novel Polymer Solutions Ltd | Methods of forming a barrier |
WO2008001102A1 (en) * | 2006-06-30 | 2008-01-03 | Novel Polymer Solutions Limited | Method of producing a polymeric material, polymer, monomeric compound and method of preparing a monomeric compound |
WO2008024509A2 (en) * | 2006-08-24 | 2008-02-28 | Mallard Creek Polymers, Inc. | Cationic latex as a carrier for bioactive ingredients and methods for making and using the same |
US20080233062A1 (en) * | 2006-08-24 | 2008-09-25 | Venkataram Krishnan | Cationic latex as a carrier for active ingredients and methods for making and using the same |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012017235A1 (en) | 2010-08-02 | 2012-02-09 | Novel Polymer Solutions Limited | Covered floors and methods of adhering flooring to a floor |
WO2012017237A1 (en) | 2010-08-02 | 2012-02-09 | Novel Polymer Solutions Limited | Composite articles and methods of producing same |
WO2012131375A2 (en) | 2011-03-31 | 2012-10-04 | Novel Polymer Solutions Limited | Window frames, structural elements for a roofed construction and methods of assembling same |
WO2013038192A1 (en) | 2011-09-13 | 2013-03-21 | Novel Polymer Solutions Limited | Mineral processing using a polymeric material that includes a moiety which selectively binds to a mineral |
US10603676B2 (en) | 2011-09-13 | 2020-03-31 | Cidra Minerals Processing Inc. | Mineral processing |
US11654443B2 (en) | 2011-09-13 | 2023-05-23 | Cidra Minerals Processing Inc. | Mineral processing |
Also Published As
Publication number | Publication date |
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JP2011502778A (en) | 2011-01-27 |
MX2010005200A (en) | 2010-08-31 |
KR20100098397A (en) | 2010-09-06 |
GB0820937D0 (en) | 2008-12-24 |
US20090174100A1 (en) | 2009-07-09 |
GB2454803A (en) | 2009-05-20 |
GB0722631D0 (en) | 2007-12-27 |
CN101861204A (en) | 2010-10-13 |
EP2219776A1 (en) | 2010-08-25 |
CA2704938A1 (en) | 2009-05-22 |
GB2454803B (en) | 2012-07-11 |
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