WO2014151543A1 - Initiateurs de polymérisation radicalaire contrôlée - Google Patents
Initiateurs de polymérisation radicalaire contrôlée Download PDFInfo
- Publication number
- WO2014151543A1 WO2014151543A1 PCT/US2014/025960 US2014025960W WO2014151543A1 WO 2014151543 A1 WO2014151543 A1 WO 2014151543A1 US 2014025960 W US2014025960 W US 2014025960W WO 2014151543 A1 WO2014151543 A1 WO 2014151543A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- independently
- group
- formula
- represented
- substituted
- Prior art date
Links
- 239000007870 radical polymerization initiator Substances 0.000 title claims description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 219
- 239000000203 mixture Substances 0.000 claims abstract description 117
- UEOGLANRPZAEAC-UHFFFAOYSA-N indeno-naphthopyran Chemical compound O1C=CC=C2C3=C4C=C(C=CC=C5)C5=C4C=CC3=CC=C21 UEOGLANRPZAEAC-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 50
- -1 acryloxy, methacryloxy Chemical group 0.000 claims description 93
- 229910052739 hydrogen Inorganic materials 0.000 claims description 69
- 239000001257 hydrogen Substances 0.000 claims description 69
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 125000005843 halogen group Chemical group 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000004423 acyloxy group Chemical group 0.000 claims description 15
- 125000005647 linker group Chemical group 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000012760 heat stabilizer Substances 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000004611 light stabiliser Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 7
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 150000002829 nitrogen Chemical class 0.000 claims description 6
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000004244 benzofuran-2-yl group Chemical group [H]C1=C(*)OC2=C([H])C([H])=C([H])C([H])=C12 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 241000907681 Morpho Species 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004197 benzothien-3-yl group Chemical group [H]C1=C(*)C2=C([H])C([H])=C([H])C([H])=C2S1 0.000 claims description 4
- 150000003950 cyclic amides Chemical class 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 4
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000004534 benzothien-2-yl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 125000005343 heterocyclic alkyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl 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])[H] 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000006684 polyhaloalkyl group Polymers 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 26
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 2
- 125000006662 (C2-C4) acyloxy group Chemical group 0.000 claims 1
- 229910014585 C2-Ce Inorganic materials 0.000 claims 1
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims 1
- 125000004986 diarylamino group Chemical group 0.000 claims 1
- 125000001188 haloalkyl group Chemical group 0.000 claims 1
- 125000003106 haloaryl group Chemical group 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 claims 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 claims 1
- 125000002755 pyrazolinyl group Chemical group 0.000 claims 1
- 125000003226 pyrazolyl group Chemical group 0.000 claims 1
- 125000001725 pyrenyl group Chemical group 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 235000013616 tea Nutrition 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 35
- 230000000670 limiting effect Effects 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 26
- 239000010410 layer Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000003431 cross linking reagent Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000002923 oximes Chemical class 0.000 description 9
- 150000003623 transition metal compounds Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 125000000466 oxiranyl group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 150000001414 amino alcohols Chemical group 0.000 description 7
- 150000003141 primary amines Chemical group 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 150000003335 secondary amines Chemical group 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000004427 diamine group Chemical group 0.000 description 5
- 229920001002 functional polymer Polymers 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 150000003077 polyols Chemical group 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 3
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 125000005641 methacryl group Chemical group 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- LFMFPKKYRXFHHZ-UHFFFAOYSA-N R24 Chemical compound C1=C(Cl)C(C)=CC=C1NC1=NC(N)=C(C=CC=C2)C2=N1 LFMFPKKYRXFHHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PNNRZXFUPQQZSO-UHFFFAOYSA-N pyran Chemical compound [CH]1OC=CC=C1 PNNRZXFUPQQZSO-UHFFFAOYSA-N 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- NGTGENGUUCHSLQ-BQYQJAHWSA-N (ne)-n-heptan-2-ylidenehydroxylamine Chemical compound CCCCC\C(C)=N\O NGTGENGUUCHSLQ-BQYQJAHWSA-N 0.000 description 1
- VRCWWHOADHLWNC-FPLPWBNLSA-N (nz)-n-heptan-3-ylidenehydroxylamine Chemical compound CCCC\C(CC)=N/O VRCWWHOADHLWNC-FPLPWBNLSA-N 0.000 description 1
- FWSXGNXGAJUIPS-WAYWQWQTSA-N (nz)-n-pentan-2-ylidenehydroxylamine Chemical compound CCC\C(C)=N/O FWSXGNXGAJUIPS-WAYWQWQTSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- ZROILLPDIUNLSE-UHFFFAOYSA-N 1-phenyl-1h-pyrazole-4-carboxylic acid Chemical compound C1=C(C(=O)O)C=NN1C1=CC=CC=C1 ZROILLPDIUNLSE-UHFFFAOYSA-N 0.000 description 1
- GFSXWQUSLTVUBW-UHFFFAOYSA-N 10bh-benzo[h]chromene Chemical compound C1=CC=C2C3OC=CC=C3C=CC2=C1 GFSXWQUSLTVUBW-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- DAUAQNGYDSHRET-UHFFFAOYSA-M 3,4-dimethoxybenzoate Chemical compound COC1=CC=C(C([O-])=O)C=C1OC DAUAQNGYDSHRET-UHFFFAOYSA-M 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- RFEBDZANCVHDLP-UHFFFAOYSA-N 3-[(4-cyanophenyl)methylamino]-6-(trifluoromethyl)quinoxaline-2-carboxylic acid Chemical compound OC(=O)C1=NC2=CC=C(C(F)(F)F)C=C2N=C1NCC1=CC=C(C#N)C=C1 RFEBDZANCVHDLP-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004171 alkoxy aryl group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000006157 aromatic diamine group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007156 chain growth polymerization reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- OSPQKQYTABCJGI-UHFFFAOYSA-N ethenyl 3,4-dimethoxybenzoate Chemical compound COC1=CC=C(C(=O)OC=C)C=C1OC OSPQKQYTABCJGI-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLVVDHDKRHWUSQ-UHFFFAOYSA-N n-heptan-4-ylidenehydroxylamine Chemical compound CCCC(=NO)CCC VLVVDHDKRHWUSQ-UHFFFAOYSA-N 0.000 description 1
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical compound CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010282 polymeric chain extension Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CYFLXLSBHQBMFT-UHFFFAOYSA-N sulfamoxole Chemical group O1C(C)=C(C)N=C1NS(=O)(=O)C1=CC=C(N)C=C1 CYFLXLSBHQBMFT-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- BIGQPYZPEWAPBG-UHFFFAOYSA-N veratric acid methyl ester Natural products COC(=O)C1=CC=C(OC)C(OC)=C1 BIGQPYZPEWAPBG-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Definitions
- the present invention relates to controlled radical polymerization
- Initiators that include a spirooxazine compound or an indenonaphthopyran compound, polymers and polymer compositions prepared therefrom, and mechanochromic articles that include such polymers and/or polymer compositions.
- Various articles, such as protective articles and support articles are typically fabricated at least In part from polymeric materials.
- Protective articles, such as helmets, safety lenses, and protective housings, and support articles, such as beams can be subjected to stresses and/or impacts that result in damage to the article, which couid lead to catastrophic failure of the article at a point in time after the damage occurred.
- the occurrence or presence of such damage is not accompanied by a visually observable indication thereof in the article.
- the damaged article would not likely be withdrawn from use, and an unexpected catastrophic failure of the article couid occur.
- Mechanochromic materials change color in response to a change in mechanical stress, such as impacts, ft is known thai mechanochromic materials can be incorporated into certain articles so as to provide a visual indication that the article has undergone a threshold mechanical stress event, which could result in catastrophic failure thereof.
- Some mechanochromic materials can undergo a reduction in stability over time, which can result in reduced mechanochromic properties, A reduction in mechanochromic properties can be accompanied by an undesirable reduction in a visually observable indication that the article in question has undergone a threshold mechanical stress event.
- a controlled radical polymerization Initiator comprising at least one radically transferable group
- the controlled radical polymerization initiator comprises at least one of, (a) a spirooxazine compound and (b) an indenonap thopyran compound, that each independently comprise at least one radically transferable group.
- n is from 1 to 4
- p is from 1 to 2
- q is from 1 to 4
- R independently for each n, R 2 independently for each p, R 3 independently for each q, R , R s , and R 6 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby! each optionally interrupted with at least one of repeatedly o ⁇ , ⁇ S ⁇ » ⁇ C(Q ⁇ -, -0(0)0-, -OC(0)0-, -S(O)-, -S0 2 -, -N(R 1 )- S and -Si(R )(R 12 ⁇ - wherein R 1 and R 12 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby!, and combinations of two or more thereof.
- the indenonaphthopyran is represented by the following Formula (If),
- x is from 1 to 4
- y is from 1 to 4
- R 7 independently for each x, R 8 independently for each y, R 9 , and R 0 are each independently setected from hydrogen, hydrocarbyi and substituted hydrocar yi each optionally interrupted with at least one of -0-, -S-, -C(Oh -C(0)O, -OC(0)0-, -S(O)-, -S0 2 - » -N ⁇ R 1 1 ⁇ -, and -Si ⁇ R 11 ) ⁇ R 12 )- wherein R" and R 12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof, and
- B and B' are each independently selected from unsubstituted aryl, substituted ary!, unsubstituted heteroaryl, substituted heteroaryl, and poiya!koxy, or B and B' taken together form a ring structure selected from unsubstituted fiuoren-9-y!idene, substituted fiuoren-9-yiidene, saturated spiro-monocyciic hydrocarbon ring, saturated spiro-bicycitc hydrocarbon ring, and spiro-tricyciic hydrocarbon ring.
- a polymer composition comprising at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, wherein each polymer prepared by controlled radical polymerization Is independently represented by the following Formula (V),
- fvl independently for each v is a residue of a monomer
- ⁇ is a residue of the controlled radical polymerization initiator that Is free of the radically transferable group
- X independently for each z, is or is derived from the radically transferable group
- w Independently for each z, is an integer of at least 2
- z is an integer of at least 1.
- the controlled radical polymerization initiator from which the polymer represented by Formula (V) Is prepared is selected from (a) the spirooxazine compound represented by Formula (I) and/or (b) the indenonaphthopyran represented by Formula (II) as described above, and in each case as described in further detail herein.
- linking groups such as divalent linking groups
- left-to-right representations of linking groups are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
- the !eft-to ⁇ right representation of the divalent linking group is inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
- molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mn) are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
- poiydispersit index (PD!) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/fvln).
- polymer means homopolymers (e.g.. prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers,
- (meth)acryiate and similar terms, such as “(meth)acry!ic acid ester” means methacrylates and/or acrylates.
- (meth)acrylic acid means methacrylic acid and/or acrylic acid,
- the terms “formed over,” “deposited over,” “provided over,” “applied over,” residing over,” or “positioned over,” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct ⁇ or abutting) contact with the underlying element, or surface of the underlying element.
- a layer “positioned over” a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
- ring position and related terms, such as “ring positions,” means a particular position in a ring structure, such as the fused ring structure, of a chemical compound, such as the spirooxazine compounds represented by Formula ⁇ 1 ⁇ and the indenonaphthopyran compounds represented by Formula (SI), and which are depicted herein in accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
- a chemical compound such as the spirooxazine compounds represented by Formula ⁇ 1 ⁇ and the indenonaphthopyran compounds represented by Formula (SI), and which are depicted herein in accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
- linear or branched groups such as linear or branched aiky!, are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear C 2 -C 2 o a!kyl groups; and groups that are appropriately branched, such as branched C 3 ⁇ C 20 alky! groups.
- hydrocarbyf and similar terms such as “hydrocarbyl subsiiiuent,” means: linear or branched C C 25 alkyi (e.g. , linear or branched d-C 10 alkyi); linear or branched C 2 -C25 alkenyl ⁇ e.g., linear or branched C 2 ⁇ C10 alkenyl); linear or branched C 2 -C 25 alkynyl (e.g., linear or branched C 2 -C 10 alkynyl); C 3 -C1 ⁇ 2 cycloalkyi (e.g., C 3 ⁇ C- i0 cycloaikyl); C3-C 12 heterocycioalky!
- C 5 -C ⁇ 8 aryi including polycyc!ic aryl groups
- C 3 -Cio aryi including polycyc!ic aryl groups
- C 5 "C 8 heteroary! having at least one hetero atom in the aromatic ring
- Ce-C 24 aralkyl e.g., C 6 -C 10 araikyl
- Representative alkyi groups include but are not limited to methyl, ethyl, propyl, isopropyi, butyl, isobutyl, sec-butyl, tert-butyi, pen ' tyf, neopentyl, hexyl, heptyi, octyi, nonyl and decyl.
- Representative alkenyl groups include but are not limited to vinyl, ally! and propenyi.
- Representative alkynyl groups include but are not limited to ethynyi, 1-propynyf, 2-propynyi, 1 -butynyl, and 2-butynyl.
- Representative cycloaikyl groups include but are not limited to cyclopropyi, cyciobutyi, cyclopentyl, cyclohexy!, and cyciooctyl substituents.
- Representative heierocyc!oa!kyi groups include buf are not limited to tetrahydrofuranyl, tetrahydropyranyl and piperidsnyi.
- Representative aryl groups include but are not limited to phenyl, naphthyl, and triptycene.
- Representative heteroary! groups include but are not limited to furanyi, pyranyl and pyridinyl.
- Representative araikyi groups include but are not limited to benzyl, and pheneihy!,
- cydoa!kyi as used herein also includes: bridged ring polycycloaiky! groups (or bridged ring polycycfic alkyl groups), such as but not limited to, bicyc!o[2.2.1]heptyl (or norbomyl) and bicyclo[2.2.2]octyl; and fused ring polycycioa!kyl groups (or fused ring polycyciic aikyi groups ⁇ , such as. but not limited to, octahydro-1 H-indenyS, and decahydronaphthaienyL
- substituted hydrocarbyl means a hydrocarbyi group in which at least one hydrogen thereof has been substituted with a group that is other than hydrogen, such as, but not limited to, halo groups, hydroxy! groups, ether groups, thiol groups, thio ether groups, carboxy!ic acid groups, carboxyiic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g...
- aikyi aikenyi, alkynyl, cycioaikyi, heterocyc!oa!kyi, aryi, heteroaryl, and araikyi groups
- amine groups such as - iRn'XR ⁇ ') where R ⁇ ' and R 2 ' are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyi,
- substituted hydrocarbyl is inclusive of halohydrocarbyl (or halo substituted hydrocarbyl) substltuents.
- halohydrocarbyl as used herein, and similar terms, such as halo substituted hydrocarbyl, means that at least one hydrogen atom of the hydrocarbyl (e.g., of the alkyl, aikenyl, alkynyl, cycioaikyi, heterocycloalkyi, aryi, heteroaryl, and araikyi groups) is replaced with a halogen atom selected from chlorine, bromine, fluorine and iodine.
- the degree of ha!ogenatton can range from at least one hydrogen atom but less than all hydrogen atoms being replaced by a halogen atom ⁇ e.g., a fluorom ethyl group), to full haiogenation (perhalogenation) in which all replaceable hydrogen atoms on the hydrocarbyi group have each been replaced by a halogen atom (e.g., trifluoromethyi or perfluoromethyi).
- a halogen atom e.g., trifluoromethyi or perfluoromethyi
- Perhalohydrocarbyl group as used herein means a hydrocarbyl group in which all replaceable hydrogens have been replaced with a halogen. Examples of perhalohydrocarbyl groups include, but are not limited to, perhaiogenaied phenyl groups and perhaiogenaied alkyl groups.
- hydrocarbyi and substituted hydrocarbyl groups from which the various groups described herein can each be independently selected such as, but not limited to, R-rRio, R 11 , R 12 , is, and R 14 can in each case be independently and optionally interrupted with at least one of -0-, -S-, -C(O)-, -C ⁇ 0)0- r -0C(0)O, -S(O)-, -S0 2 -, -N(R 11 )- and -Si(R 1 t )(R 12 )-.
- interrupted with at least one of - ⁇ -, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(0 ⁇ , ⁇ S0 2 -, -N(R 11 )-, and -Si(R 11 )(R 12 )- means that at least one carbon of, but less than all of the carbons of, the hydrocarbyi group or substituted hydrocarbyi group, is in each case independently replaced with one of the recited divalent non-carbon linking groups.
- the hydrocarbyi and substituted hydrocarbyi groups can be interrupted with two or more of the above recited linking groups, which can be adjacent to each other or separated by one or more carbons.
- a combination of adjacent - C(0) ⁇ and -N(R 11 ⁇ - can provide a divalent amide linking or interrupting group, ⁇ C(Q)- N(R 1 ⁇
- a combination of adjacent - N(R 11 ⁇ -, -C(Q - and -O- can provide a divalent carbamate (or urethane) linking or interrupting group, ⁇ N(R 11 )-C(0)-0-, where R 11 Is hydrogen.
- mechanochromic and similar terms, such as “mechanochramic compound” means having an absorption spectrum for at least visible radiation that varies in response to mechanical stress.
- mechanochramic material means any substance that is adapted to display mechanochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies In response to mechanical stress) and which includes at least one mechanochromic compound, at least one polymer, and/or a polymer composition according to the present invention,
- the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention are, with some embodiments, capable of converting from a first state, for example a "clear state * ' or a "colorless state” to a second state, for example a "colored state,” in response to mechanical stress.
- a first state for example a "clear state * ' or a "colorless state”
- a second state for example a "colored state”
- the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention undergo minimal, or are substantially free of, reversion back to the previous state (such as a clear or colorless state) after exposure to and optional removal of the mechanical stress.
- the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties.
- the first state and the second state of a mechanochromic compounds, polymers, polymer compositions, and articles of the present invention cars differ with respect to at least one optica! property, such as but not limited to the absorption of visible and/or UV radiation.
- the mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can have a different absorption spectrum in each of the first and second state.
- a mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can be clear in the f rst state and colored in the second state.
- mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can have a first color in the first state and a second color in the second state.
- actinic radiation means electromagnetic radiation that is capable of causing a response In a material, such as, but not limited to, transforming a photochromic material from one form or state to another state, or initiating polymerization.
- film means a pre- ormed layer having a generally uniform thickness thai is not capable of self-support.
- sheet means a pre-formed layer having a generally uniform thickness that is capable of self-support.
- coating means a supported film derived from a flowable composition, which can have a uniform thickness or non-uniform thickness, and specifically excludes polymeric- sheets and unsupported polymer films.
- a coating that includes one or more mechanochromic polymers or compositions of the present invention can, with some embodiments, be a mechanochromic coating,
- controlled radical polymerization and related terms such as "controlled radical polymerization method(s)” includes, but is not limited to, atom transfer radical polymerization (ATRP), single electron transfer polymerization (SETP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization (N P).
- ATRP atom transfer radical polymerization
- SETP single electron transfer polymerization
- RAFT reversible addition-fragmentation chain transfer
- N P nitroxide-mediated polymerization
- Controlled radical polymerization such as ATRP, is described generally as a "living polymerization," i.e., a chain-growth polymerization that propagates with essentially no chain transfer and essentially no chain termination.
- the molecular weight of a polymer prepared by controlled radical polymerization can be controlled by the stoichiometry of the reactants, such as the initial concentration of monomer(s) and initiators), in addition, controlled radical polymerization also provides polymers having characteristics including, but not limited to: narrow molecular weight distributions, such as pofydispersity Index (PDl) values less than 2.5; and/or well defined polymer chain structure, such as block copolymers and alternating copolymers, with some embodiments.
- PDl pofydispersity Index
- the ATRP process is described in further detail as follows.
- the ATRP process can be described generally as including: polymerizing one or more radically polymerizable monomers in the presence of an initiation system; forming a polymer; and isolating the formed polymer.
- the initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates In a reversible redox cycle with the Initiator; and a ligand, which coordinates with the transition metal compound.
- the ATRP process is described in further detail In U.S, Pat. Nos.
- the polymers and polymer compositions of the present invention prepared by controlled radical polymerization are prepared generally in accordance with the ATRP method disclosed at column 4, line 12, through column 5, line 67 of United States Patent No. 6,265,489 B1 , which disclosure is incorporated herein by reference.
- controlled radical polymerization Initiators having at least one radically transferable group, in which the controlled radical polymerization initiators include at least one spirooxazine compound represented by Formula (I), and/or at least one indenonapbthopyran compound represented by Formula (li), as described previously herein,
- the controlled radical polymerization Initiators of the present invention are each independently mechanochromic controlled radical polymerization Initiators.
- polymers prepared from the controlled radical polymerization Initiators of the present invention are mechanochromic polymers
- polymer compositions that include the polymers of the present invention are mechanochromic polymer composition.
- articles that include the polymers of the present invention are mechanochromic articles.
- the controlled radical polymerization initiators of the present invention can, with some embodiments, each independently have at least one radicall transferable group, such as from 1 to 20, or from 1 to 15, or from 1 to 10, or from 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2 radically transferable groups.
- the controlled radical polymerization initiators of the present Invention each independently have at least 2 radically transferable groups, such as from 2 to 20, or from 2 to 15, or from 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3.
- each controlled radical polymerization initiator of the present invention independently has two (2) radically transferable groups,
- the spirooxazine represented by Formula (I) at least one of Ri Independently for each n, and RJI independently for each p, Independently include the first radically transferable group; and at least one of R 3 independently for each q, R 4 , R. s and R 6 independently comprise the second radically transferable group.
- Each first radically transferable group and each second radically transferable grou can be the same or different.
- each first radically transferable group is positioned so as to be on one side of the spirooxazine relative to bond (a ' ) ⁇ at least one R, and/or at least one R 2 each independentl including a first radically transferable group), and each second radically transferabie group is positioned so as to be on the other side of the spirooxazine relative to bond (a') (at least one R 3 , and/or R 4l and/or R 5 , and/or Re each independently include a second radically transferable group),
- Each first radically transferable group and each second radically transferable group can be the same or different.
- each first radically transferable group is positioned so as to be on one side of the indenonaphthopyran relative to bond (a) (B and/or B' each independently including a first radically transferable group), and each second radically transferable group is positioned so as to be on the other side of the indenonaphthopyran relative to bond (a) (at least one R 7 , and/or at least one R 8 , and/or R 9s and/or R-io each Independently include a second radically transferable group).
- the spirooxazine represented by Formula (!) includes one first radically transferable group, and one second radically transferrabie group.
- R or R ? Includes the first radically transferable group; and one of R 3 , R 4 , R 5 , and R 6 includes the second radically transferable group,
- B or B' includes the first radically transferable group; and one of R 7> R s , Rg, and R 0 includes the second radically transferable group.
- the spirooxazine represented by Formula (I) includes, with some further embodiments, one first radically transferable group, and one second radically transferrabie group,
- one R 2 includes the first radically transferable group
- one R 3 includes the second radically transferable group
- the indenonaphthopyran represented by Formula (ii), with some embodiments, includes one first radically transferable group, and one second radically transferable group.
- 8 or 8' includes the first radically transferable group; and one R 7 or one R s Includes the second radically transferable group.
- Each radically transferable group of the controlled radical polymerization initiators of the present Invention can each be independently selected from one or more atoms or groups that are radically transferable under controlled radical polymerization conditions.
- the Rf group ⁇ of OR f is linear or branched C C 20 alky! group, in which at least one hydrogen group is optionai!y substituted with a halo group, such as F or CI).
- Each R 9 is Independently selected from ary! or a linear or branched CrC 20 alkyl group. With the N ⁇ R 9 ) 2 group, the R s groups can loin to form a 5-, 6- or 7-membered heterocyclic ring.
- each radically transferable group of the controlled radical polymerization initiators of the present invention are independently selected from CI, Br, and 1, With some further embodiments, each radically transferable group of the controlled radical polymerization initiators of the present invention is Br.
- R- t , R 2> R 3 , R, 5 , R 5 , and R 6 independently include, or is, a group represented by the Formula (ill), and described in further detail below.
- R 7 , Rs, Rg, io. B, and B' each independently include, or is, a group represented by the following Formula (III);
- R 3 is a divalent linking group selected from a bond, a divalent hydrocarbyi group and a divalent substituted hydrocarbyi group each optionally interrupted with at least one of -0-, ⁇ S ⁇ , -C(O)-, -0(0)0-, ⁇ 0C(0)0 ⁇ , -8(0)-, -SQr, -N(R 15 )- and -Si(R s )(R 16 )- and combinations of two or more thereof.
- R 15 and R 1e groups are in each case independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi.
- R is a divalent linking group selected from a bond, divalent hydrocarbyi, and divalent substituted hydrocarbyi and X is the radically transferable group.
- R 13 is selected from a bond, divalent C C 2 o linear or branched alkyl divalent C-s-C ⁇ cyciic a!kyl, divalent C 3 -C 10 heterocyclic alkyl, divalent aryi, divalent heteroaryi, and combinations thereof optionally interrupted with at least one of -O- and -S- and combinations of two or more thereof.
- R 14 is selected from divalent CrC 2 ⁇ > linear or branched alkyl, and X is selected from a halo group,
- R 3 is selected from a bond, divalent C r C 0 linear or branched alkyl, divalent C 3 -Ci 0 heterocyclic aikyi, divalent aryi, and combinations thereof optionally interrupted with at least one of -0-.
- R 14 is selected from divalent CrC-io linear or branched alkyl, and the halo group from which X is selected is CI, Br, or I.
- the divalent linking group R 3 is bonded directly to the spirooxazine represented by Formula (I).
- the divalent linking group i 3 of Formula (III) can, with some embodiments, be bonded to another group that is bonded to the spirooxazine represented by Formula (I), such as R-i, R 2 , R 3 , R 4 , R 5 , and/or R 5 .
- the divalent linking group R 13 of the group represented by Formula (III), with some embodiments, is bonded directly to the indenonaphthopyran represented by Formula (II).
- the divalent linking group R 13 of Formula (III) can, with some embodiments, be bonded to another group that Is bonded to the indenonaphihopyran represented by Formula ⁇ !( ⁇ , such as R 7l R 8 , R 8 , R 1C) B, and/or B ! .
- one 2 independently includes, or is, the group represented by Formula (IH), and one R 3 Independently includes, or is, the group represented by Formula (III),
- one R 2 independently includes, or is, the group represented by Formula (111), which is bonded to ring position 5' of the spirooxazine represented by- Formula (I);
- one R 3 independently includes, or is, the group represented by Formula (Hi), which bonded to ring position 5 of the spirooxazine represented by Formula (i); and the remaining groups R,, R 2 , R 3 , R , R 5 , and R 6 are free of the group represented by Formula (ill).
- one 8 or 8' Independently includes, or is, the group represented by Formula (Hi)
- one R 7 or R s Independently includes, or is, the group represented by Formula (III).
- one B or B * at ring position 3 independently includes, or is, the group represented by Formula (Hi); one Re independently includes, or is, the group represented by Formula (ill), which is bonded to ring position 1 1 of the Indenonaphihopyran represenied by Formula (II); and the remaining groups B or 8', R 7 , R 8 , Rg, and R 10 are free of the group represented by Formula (ill).
- the group represented by Formula (III) is selected from one or more groups represented by the following Formulas (l!i-A) through (ifi-F)
- X In each case is independently a radically transferable group, such as a halo group, such as CI, Br, or I.
- 3 ⁇ 4 independently for each n and R 2 independently for each p are each independently selected from hydrogen, ary!, mono ⁇ CrC 6 )a!koxyaryl, di(Ci-C6)a)koxyary!, mono(CrC 6 )aikylaryl, di(CrC 6 )alkyiaryl, bromoaryl, ch!oroaryl, fiuoroaryl, C3-C7 cycloalkylaryi, C 3 ⁇ C 7 cyc!oa!kyl, C3-C7 cyc!oa!ky!oxy, C3-C7 cycioaikytoxy(Ci-C8)alkyi, C3-C7
- aryioxy(C-i -C 6 )alky! aryioxy(CrC6>a!koxy, mono- or ds(C r Cg)a!kylary1 ⁇ Ci-C 6 ⁇ alkyl, mono- -or diCCi -C 6 )alkoxyafy!(Cr C 6 )a!kyi, mono- or di(Ci-C 6 ⁇ alkyiaryl(C r C 6 )a!koxy, mono- or di(Ci 1 ⁇ 4)a!koxyaryi ⁇ CrC 6 )aikoxy, amino, mono(CrC 6 )aikyfanriino, d!(CrC 6 )aikylarrtino, dsarylamino, N-(Ci-C 6 )alkylp!perazino, N-arylpiperazino, aziridino, indoiino, piperidino, aryfpiperidino, ary
- R 3 of the spirooxazine represented by Formula (I) is, independently for each q, chosen from hydrogen, C 1 -C5 alkyi, d-C 5 aikoxy, nitro, cyano, Ci-C 8 a!koxycarbonyl, acyloxy(C,- C 6 alkyi), acyioxy(C 3 ⁇ C 7 cycloalkyl), acyioxy(aryl),, halo, C C monohaloaiky! or C r C 4 polyhaloalkyl; said halo substiiuenis being chioro, fiuoro, iodo or bromo.
- R 4 of the spirooxazine represented by Formula (I) is chosen from hydrogen, Ci ⁇ C 8 alkyl, C3-C7 cycloalkyl, phen ⁇ C C )alkyl, naphth ⁇ Ci-C 4 )alkyl, ally!, acryiylpxy(C 2 -C 6 )alkyl, methacrylyloxy(C 2 -C 6 )alkyi > C 2 -C 4 acyioxy ⁇ C 2 -C 6 )aikyl, carboxy ⁇ C 2 -C 6 )a!kyl, eyano(C 2 - C 6 )alkyi, hydroxy(C 2 -C 8 )alky!, triarylsilyi, triaryisilyioxy, tri(C Ce)aiky!silyi,
- R 5 and e of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, C r C 5 alkyl, acyloxy ⁇ C C 6 alkyl), acyfoxy(C 3 -C 7 cycloalkyl), acyloxy ⁇ ary1), benzyl, phenyl, mono- or di-substiiuted phenyl, said phenyl substituents being Ci-C 5 alkyl or C C 5 aikoxy; or R s and R 6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
- Ri independently for each n and R 2 independently for each p are each independently selected from hydrogen, aryl, rnono ⁇ CrC 6 )alkoxyaryl, di(Ci-C e )a!ky1amirso, piperklino, morpho!ino, Ci-C 6 aikoxy, or fluoro.
- R 3 of the spirooxazine represented by Formula (I) is, independently for each q, selected from hydrogen, C r C 5 alky!, Ci-C 5 aikoxy, C C 8 aikoxycarbonyi, acy!oxy ⁇ CrCs aikyl), acyjoxy ⁇ C3-C? cycloafkyi), acy!oxy(aryi),, halo, Ci ⁇ C monohaioa!kyi or C C poiyhaloaikyi; and said ha!o substituents being chloro or fluoro.
- R 4 of the spirooxazine represented by Formula (!) is selected from hydrogen, C C 8 aikyl, phen(C r -C 4 )alkyi, acryiyfoxy ⁇ C 2 -C8)a!kyl, methacryiy!oxy(CrC 6 )a!ky!,
- R 5 and R 6 of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, Ci-C 5 aikyl, phenyl; or R s and R 6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
- R 7 independently for each x and R s independently for each y are each independently selected from; hydrogen; a compatibiizing substituent; halogen selected from fluoro and chloro; Ci ⁇ C 2 o atkyi; C 3 - Cio cycloaikyl; acyioxy(C G 6 aikyl), acy!oxy(C 3 -C 7 cycloaikyl), acyioxy(aryi); substituted or unsubstituted phenyl, the phenyl substituents being selected from hydroxy!, halogen, carbonyl, C -C 20 aikoxycarbonyi, cyano, halo(CrC 2 o)aikyl, C C 2 o aikyl or Ci-C 20 aikoxy; -G-R 10 ' or -C ⁇ 0)-R 1c Or wherein
- substituted phenyl(C C 2 o)a!kyl mono(CrC 20 )aikoxy substituted phenyl ⁇ C r C 2 o)alkyf, (d -C 20 ⁇ aikoxy(C 2 -C 2 o)a!kyl, C 3 - C 10 cycloaikyl, or mono(Ci ⁇ C 20 )alkyi substituted C 3 -C 10 cycloaikyl;
- R ⁇ ' and R 12 are each independently hydrogen, Ci-C 20 aikyl, phenyl, naphfhyi, furanyl, benzofuran-2 ⁇ yl, benzofuran-3 ⁇ yl ( thienyl, ⁇ benzothien-2-y!, .benzothien-3-yl, dibenzofuranyi, dibenzothienyl, benzopyridyi, fiuorenyl, Ci-C 2Q alky!aryl, C 3 -Ci 0 cycioaikyi, CrC 2G bicycloaikyl, C 5 - C 20 tricyc alkyl or Ci- C w alkoxyafkyf, wherein said aryi group is phenyl or naphthyl, or Rn' and R 2 * come together with the nitrogen atom to form a C 3 -C 20 hetero-bicycloaikyl ring or a C 4 -C 20 hetero-tricyc!o
- R 7 independently for each x and R 8 independently for each y are each independently selected from a nitrogen containing ring represented by the following graphic Formula (IVA),
- each -V- is independently chosen for each occurrence from -CH 2 - ( -CHiR-ia )-, ⁇ C(R 13 ! ) 2 - ⁇ -CH(aryi)-, ⁇ C(aryl) 2 ⁇ , and - C ⁇ R 13 ')(aryl)-, and Z is -Y-, -0-, ⁇ S ⁇ , -3(0)-, -S0 2 -, -NH-, -N(R 13 ')-, or -N(aryl)-, wherein each R 3 ' is independently C1-C 20 aikyi, each aryi is independently phenyl or naphthyl, m is an integer 1 , 2 or 3, and p is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is ⁇ .
- R 7 independently for each x and R@ independently for each y are each independently selected from a group represented by one of the following graphic Formulas (IVB) or (iVC):
- Ri 5 , R 6 , and R 17 are each independently hydrogen, d-Ce aikyi, phenyl, or naphthyl, or the groups R 15 and R3 ⁇ 4 6 together form a ring of 5 to 8 carbon atoms and each R d is independentiy for each occurrence selected from C r -C 20 aikyi, Ci-C 20 alkoxy, fluoro or chioro, and Q is an integer 0, 1 , 2, or 3.
- R 7 Independently for each x and R s independently for each y are each independently selected from unsubstiluted, mono-, or di-substiiuted C 4 -C 1g spirobicyciic amine, or unsubstituted, mono-, and di- substituted C4-C18 spirotri cyclic amine, wherein said substituents are independently aryi, C C 2 o aikyi, C r C 2 o aikoxy, or phenyi(C 1 ⁇ C 2 o)aikyi.
- T and T are each independently oxygen or the group -NRn'-, where R ⁇ ', R 5 , and R 6 are as set forth above.
- R 9 and R 0 are each independently selected from the following classes of groups (i) through (v).
- R 9 and R 10 of Formula (II) are each independently selected from, (i) hydrogen, C C 20 aikyi, C -C 20 haioalkyi, C 3 ⁇ C 0 cycloa!ky!, acyloxy(Ci-0 6 aikyi), acyfoxy(C 3 -C7 cycloa!kyl), acyioxy(aryl), ailyi, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C1-C20 aikyi or CrC 20 aikoxy.
- R 9 and R 10 of Formula (il) are each independently selected from, (il) an unsubstituted, mono- di-or tri-substituted group chosen from phenyl, naphthyl, phenanthryi, pyren l, quinoiyl, isoquinolyl, benzofuranyl, thienyl, benzofbienyl, dtbenzofuranyl, dibenzothienyl, carbazoiyi, or indoly!, said group substituents in each case being independently chosen from halogen, C C 20 aikyi or C C 2 Q aikoxy.
- R g and R 10 of Formula (il) are each independently selected from, (ill) mono-substituted phenyl, said substiiuent located at the para position being - ⁇ CH 2 ) or ⁇ 0-(CH 2 ) ⁇ , wherein t is the intege 1 , 2, 3, 4, 5 or 6, said subsiituent being connected to an ary! grou which is a member of a photochromic material.
- F3 ⁇ 4 and 0 of Formula ⁇ !!) are each independently selected from, (iv) the group ⁇ CH(R 10 )G, wherein R 18 is hydrogen, d-Cr, aiky! or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, and G is -Cr ⁇ OR 19 , wherein R 19 is hydrogen, -C(0)R 10 , C C 2 o alkyt, C -C 20 aikoxy(Cr'C2o)aSkyl, pheny1(C C 20 ⁇ a!kyl, mono(C C3 ⁇ 4))aikoxy substituted pheny!(Ci- C 2 o)alkyl, or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being C
- R 9 and R 0 together form a spiro subsiituent selected from a substituted or unsubstituted spiro-carbocyciic ring containing 3 to 6 carbon atoms, a substituted or unsubstituted spiro-heterocyc!ic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms Including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyc!Ec ring being anrte!iated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C Czc aikyi.
- B and 8' are each independently: an aryl group that is mono-substituted with a compatiblizing
- a substituted phenyl a substituted aryl; a substituted 9-juloilndinyl; a substituted heteroaromatic group chosen from pyridyl, furantyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,
- dibenzoihienyl, carbazoyi, benzopyridyi, indolinyi, and fiuorenyi wherein the phenyl, aryl, 9 ⁇ ju blind inyL or heteroaromatic substituent is a reactive subsiituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9-ju!o!idinyf; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyf, furanyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yi, benzotbien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyi, benzopyridyi, indoiinyl, and fiuorenyi.
- the phenyl, aryl and heteroaromatic substituents, from which B and B' can each be independently selected, are in each case independently: hydroxy!, a group -C ⁇ 0)R 2 i, wherein R 21 is -OR 22l ⁇ N(R 23 )R 2 4, piperidino, or morpho!ino, wherein R22 is aiiyl, C r -C 20 aikyl, phenyl, mono(Ci-C 2 o)aikyi substituted phenyl, mono(Ci- C 20 )aikoxy substituted phenyl, pbenyl(C r -C 20 )alky!, mono ⁇ CrC 20 )aiky!
- B23 and R 24 are each independently C1-C20 alkyf, C 3 -C 0 cyc!oaikyl, phenyl or substituted phenyl, the phenyl substituenis being C1-C20 a!ky!
- B and B ' are each independently an unsubststuted or mono-substituted group chosen from pyrazo!y!, imidazoiyl, pyrazoiinyi, imidazollnyl, pyrrolinyi, phenothiaziny!, pbenoxazinyl,
- phenaziny! and acridinyl.
- substituenis are, with some embodiments, Ci-C 20 alkyl, C1-C20 aikoxy, phenyl, or halogen.
- B and B' are each independently a roup represented by one of:
- K is -CH 2 - or -0-, and is -O- or substituted nitrogen, provided that when M is substituted nitrogen, K is - CH 2 -, the substituted nitrogen substituents being hydrogen, d-Cao alkyl, or CrC 20 acyi, each R 25 being independently chosen for each occurrence from CrC 20 aikyi, C r C 2 o aikoxy, hydroxy, and halogen, R 26 and R 2 each being independently hydrogen or C C 2 o alkyl, and u Is an intege ranging from 0 to 2.
- B and B' are each independently, a group represented by:
- F1 ⁇ 2 is hydrogen or C r C20 aikyl
- R 2 g is an unsubstituted, mono-, or di-substituted group chosen from nap thyi, phenyl, furanyi, and thienyl, in which the substituents are C1-C2 0 aiky!, C C 2 o alkoxy, or haiogen,
- R 7 independently for each x and R B independently for each y, of the indenonaphthopyran represented by Formula (II), are each independently selected from, hydrogen, Ci ⁇ C 6 aikyl, C3-C7 cycioalkyi, morphoiino, morphoiino substituted with Ci-C 8 linear or branched aikyl, C Ce haioalky!, fiuoro, chioro, and -O-R 10 '.
- R 9 and R 10 of the indenonaphthopyran represented by Formula ( ⁇ ), are each independently selected from hydrogen, Cr-Cg aikyl, C Cg haloaikyi, and C3-C7 cycioalkyi, or together form a spiro substiiuent selected from a substituted or unsubstituted spi o-carbocyclie ring containing 3 to 8 carbon atoms.
- 8 and 8', of the indenonaphthopyran represented by Formula (II), are each Independently selected from aryi, ary! substituted with C- r C 6 alkoxy, and aryi substituted with morphoiino,
- R 7 and R 8 can each be independently selected from a compatibilizing substiiuent; and B and B : can each be selected from an aryi group that is mono-substituted with a compatibilizing substiiuent. If the indenonaphthopyran includes multiple compatibilizing substituents, each compatibilizing substiiuent can be independently chosen.
- Each compatibilizing substiiuent can independently be represented by one of the following;
- Non-limiting examples of groups that ' -D- can represent according to various non-limiting embodiments include a diamine residue or a derivative thereof, wherein a first amino nitrogen of said diamine residue can form a bond with -A'-, or a substituent or an available position on the indeno-fused naphthopyran, and a second amino nitrogen of said diamine residue can form a bond with -E-, -G- or -J; and an amino alcohol residue or a derivative thereof, wherein an amino nitrogen of said amino alcohol residue can form a bond with ⁇ A' ⁇ , or a substituent or an available position on the indeno-fused naphthopyran, and an alcohol oxygen of said amino alcohol residue can form a bond with - ⁇ --, -G- or ⁇ j.
- the amino nitrogen of the amino alcohol residue can form a bond with -E-, -G- or -J
- the alcohol oxygen of the amino alcohol residue can form a bond with -A'-, or a substituent or an available position on the indenonap ' hthopyran.
- Non-limiting examples of suitable diamine residues that -O- can represent include an aliphatic diamine residue, a cycio aliphatic diamine residue, a diazacycloalkane residue, an azacyclo aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue, More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-llmlting embodiments disclosed herein include the following:
- Non-limiting examples of suitable amino alcohol residues that -D- can represent include an aliphatic amino alcohol residue, a cycio aliphatic amino alcohol residue, an azacyclo aliphatic alcohol residue, a diazacycio aliphatic alcohol residue and an aromatic amino alcohol residue, More particular, illustrative and non-limiting examples of amino alcohol residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following;
- -E- can represent a dicarboxyiic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxyiic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxyiic acid residue can form a bond with -G-.
- suitable dicarboxyiic acid residues that -E- can represent include an aliphatic dicarboxyiic acid residue, a cyc!oa!iphatic dicarboxyiic acid residue and an aromatic dicarboxyiic acid residue. More particular, illustrative and non-limiting examples of dicarboxyiic acid residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
- ⁇ G- can represent a group represented by the following general formula
- oxygen of the polyo! residue forms a bond with a group - ⁇ .(OC 2 H 4 )x(OC 3 H 6 ) y ⁇ OC 4 H 8 )J- (i.e., to form the group 4(00 2 ⁇ 4 ) ⁇ (00 3 ⁇ ⁇ ) ⁇ (OC 4 H B ) 2 K3-) 1 and the second polyo! oxygen forms a bond with -E- or -J.
- suitable poiyoi residues that -G ⁇ can represent include an aliphatic poiyoi residue, a cycio aliphatic poiyoi residue and an aromatic poiyoi residue,
- poiyois from which the poiyoi residues that -G- can represent can be formed according to various non-limiting embodiments disclosed herein include (a) low molecular weight poiyois having an average molecular weight less than 500, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col, 4, lines 48-50, and co!. 4, line 55 to col, 8, line 5, which disclosure is hereby specifically incorporated by reference herein: (b) polyester poiyois, such as, but not limited to, those set forth in U.S. Patent No. 8,555,028 at col.
- -J can represent a group - , wherein - represents a group such as, but not limited to, -CH z COOH, ⁇ CH(CH 3 )COOH, -C(OXCH 2 ⁇ w COOH, -C 6 H 4 S0 3 H, -C 5 H 10 SO 3 H, -C 4 H 8 S0 3 H, -C 3 M 6 S0 3 H, -C 2 H 4 SO 3 H and ⁇ S0 3 H, wherein " " ranges from 1 to 18.
- ⁇ J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH.
- -J can represent hydrogen, provided that if ⁇ J represents hydrogen, -J is bonded to an oxygen of ⁇ D- or -G-, or a nitrogen of --D-.
- ⁇ J can represent a group -L or residue thereof, wherein -L can represent a reactive moiety.
- -L can represent a group such as, but not limited to, acry!, methacryl, croty!, 2- (methacryloxy)ethyicarbarnyi, 2- ⁇ methacryloxy ⁇ ethoxycarbony!, 4-vinylphenyi. vinyl, 1-chlorovinyl or epoxy.
- the terms aory!, methacryl, crotyl, 2- (rnethacryioxy)ethylcarbaroyl, 2-(methacryloxy)eihoxycarbonyl, 4-vinyiphenyl, vinyl, 1-chlorovm l, and epoxy refer to the following structures:
- -G- can represent a residue of a polyoi, which Is defined herein to include hydroxy-containlng carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at col. 7, line 56 to coi. 8, line 17, which disclosure Is hereby specifically incorporated by reference herein.
- the poiyol residue can be formed, for example and without limitation herein, by the reaction of one or more of the po!yol hydroxyl groups with a precursor of -A'-, such as a carboxylic acid or a methylene halide, a precursor of po!yalkoxylated group, such as polyalkyiene glycol, or a hydroxy!
- the polyoi can be represented by « ⁇ (OH) a and the residue of the polyoi can be represented by the formula -0-g ⁇ (OHJ a .-, wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
- one or more of the poiyol oxygens of -G- can form a bond with -j (i.e., forming the group -G-J),
- -j i.e., forming the group -G-J
- the reactive and/or compatibilizing substituent comprises the
- ⁇ J represents a group ⁇ K that contains a suifo o sulfono terminating group
- -G-J can be produced by acidic condensation of one or more of the polyoi hydroxy! groups with HOC 6 H 4 S0 3 H; HOC 5 H 10 SO 3 H; HOC 4 H 8 S0 3 H; HOC 3 H 6 S0 3 H; HOC 2 H 4 S0 3 H; or H 2 SO 4 , respectively.
- -G- represents a polyoi residue
- -J represents a group -L chosen from acry!
- methacryl 2-( efnacryioxy)ethylearbamy1 and epoxy
- -L can be added by condensation of the poiyof residue with acryi y! chloride, methacryloyl chloride, 2 ⁇ isocyanatoethyl methacryiate o epichlorohydrin, respectively.
- the spirooxazine compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the spirooxazine compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 6,019,914 at column 9, lines 7-48, which disclosure is incorporated herein by reference.
- the spirooxazine compounds of the present invention are prepared in accordance with the synthetic descriptions provided in the examples further herein.
- the indenonaphthopyran compounds of the present invention can be prepared by art-recognized methods.
- the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No, 6,296,785, at column 10, line 52 through column 29, line 18, which disclosure is incorporated herein by reference.
- the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 7,527,754 B2 at column 13, line 52 through column 14, line 62, which disclosure is incorporated herein by reference.
- the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 5,645,767, at column 5, line 6 through column 1 1 , line 31 which disclosure is incorporated herein by reference.
- the indenonaphthopyran compounds of the present invention are prepared in accordance with the synthetic descriptions provided In the examples further herein.
- the present invention also relates to a polymer composition that includes at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, in -which each polymer prepared by controlled radical polymerization is independently represented by Formula (V) as described previously herein,
- the controlled radical polymerization initiator is selected from a spirooxazine represented by Formula (I), and an indenonaphthopyran represented by Formula (l!), which are each as described previously herein.
- the ATRP process can be described generally as Including: polymerizing one or more radically polymerlzable monomers in the presence of an initiation system; forming a polymer; and Isolating the formed polymer.
- the initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates in a reversible redox cycle with the initiator; and a iigand, which coordinates with the transition metal compound.
- the initiator used to prepare the polymers of the polymer compositions of the present invention, includes the spirooxazine compound represented by Formula (i) and/or the indenonaphthopyran compound represented by Formula (!l), with some embodiments.
- Catalysts that can be used with some embodiments in preparing polymers, by controfled radical polymerization (such as ATRP), include any transition metal compound that can participate In a redox cycle with the initiator and the growing polymer chain. With some embodiments, the transition metal compound is selected such that It does not form direct carbon-metal bonds with the polymer chain. Transition metal catalysts useful in the present invention can be represented by the following Formula (VI),
- TM represents the transition metal
- t is the formal charge on the iransition metal having a value of from 0 to 7
- X Is a countenon or covalently bonded component
- the transition metal (TM) include, but are not limited to, Cu, Fe, Au, Ag, Hg, Pd, Pi, Co, Mn, Ru, Mo, b and n
- Examples of X include, but are not limited to, halogen, hydroxy, oxygen, C r C 5 - afoxy, cyano, cyanato, thiocyanato and azido.
- the transition metal is Cu(l) and X is a halogen, such as chloride.
- a class of transition metal catalysts are the copper ha!ides, such as Cu(!CI.
- the transition metal catalyst contains a small amount, such as 1 mole percent, of a redox conjugate, for example, Cu(H)CI 2 when Cu(l)CI is used,
- 0131J Llgands that can be used in preparing the polymers of the present Invention, by controlled radical polymerization include, but are not limited to compounds having one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, which can coordinate to the transition metal catalyst compound, such as through sigma and/or pi bonds.
- Classes of useful ligands include but are not limited to: unsubsiituted and substituted pyridines and bipyridines; porphyrins; eryptands; crown ethers, such as 18-crown-6; polyamines, such as ethylenedlamine; glycols, such as aikyiene glycols, such as ethylene glycol; carbon monoxide; and coordinating monomers, such as styrene, acryionitrile and hydroxya!kyi (meth)acrylates.
- the Hgand is selected from one or more substituted bipyridines, such as 4,4'-dialky!bipyridy!s.
- the amounts and relative proportions of initiator, transition metal compound and llgand are those for which ATRP is most effectively performed.
- the amount of initiator used can vary widely and is typically present In the reaction medium in a concentration of from 10 '4 moles/liter (M) to 3 M, such as, from 10 "3 M to 10 "1 M.
- M molecular weight
- the molar ratio of initiator to monomer can be an important factor in polymer preparation, with some embodiments.
- the molar ratio of initiator to monomer is, with some embodiments, within the range of 1G ⁇ 4 :1 to 0.5:1 , or 10 "3 :1 to 5x10 "2 :1.
- the molar ratio of transition metal compound to initiator is, with some embodiments, In the range of 10 "4 :1 to 10:1, or 0,1 :1 to 5:1.
- the molar ratio of iigand to transition metal compound Is with some embodiments, within the range of 0.1 :1 to 100:1 , or 0.2:1 to 10:1.
- subscript z is an integer of at least 1 , such as from 1 to 10, or 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2.
- Subscript z is at least 2, such as fro 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3, or 2.
- subscript z is equal to the number of radically transferable groups present on the controlfed radical polymerization initiator.
- subscript is an integer of at least 2, such as from 2 to 1000, or from 2 to 500, or from 2 to 300, or from 2 to 200, or from 2 to 100, or from 2 to 50, or from 2 to 40, or from 2 to 30, or from 2 to 25, or from 2 to 20, or from 2 to 10, or from 2 to 5,
- X independently for each z, is or is derived from the radically transferable group that was originally bonded to the controlled radical polymerization Initiator.
- the radically transferable group(s) of the controlled radical polymerization initiator such as the spirooxazine compound represented by Formula (1) and the indenonaphthopyran represented by Formula (II) ⁇ is a halo group, such as Br
- the X can be the radically transferable bromo group (Br), with some embodiments.
- the radically transferable group can, with some embodiments, optionally be (a) removed, or (b) chemically converted to another moiety.
- the symbol X is considered herein to be derived from the radically transferable group of the initiator.
- the radically transferable group can be removed by substitution with a nucfeophi!tc compound, such as an alkali metal aikoxyiate, with some embodiments.
- the method by which the radically transferable group is either removed or chemically converted is relatively mild with regard to the reactive functionality of the polymer. Many nucleophiJic substitution reactions can result in loss of reactive functionality from the polymer.
- the polymer has oxirane functionality, which can be lost in the presence of a nucleophile, such as an alkali metal aikoxyiate.
- the halogen when the radically transferable group i.s a halogen, the halogen can be removed by a mild dehalogenation reaction, which does not reduce sensitive functionality of the polymer, if any (such as oxirane functionality, with some embodiments).
- the reaction is typically performed as a post-reaction after the polymer has been formed, and in the presence of at least an ATRP catalyst.
- the dehalogenation post-reaction is performed In the presence of both an ATRP catalyst and its associated ligand.
- the mild dehalogenation reaction is performed by contacting the halogen terminated polymer of the present invention: with one or more ethylenically unsaturated compounds, which are not readily radically po!ymerizab!e under at least a portion of the spectrum of conditions under which controlled radical polymerizations, such as atom transfer radical polymerizations, are performed, hereinafter referred to as "limited radically polymeri convincede ethySenically unsaturated compounds" (LRPEU compound).
- LRPEU compound limited radically polymeri convincede ethySenically unsaturated compounds
- the reaction between the halogen terminated polymer and one or more LRPEU compounds results int. (1 ) removal of the terminal halogen group; and (2 ⁇ the addition of at least one carbon-carbon double bond where the terminal carbon-halogen bond Is broken.
- the dehalogenation reaction Is typically conducted at a temperature in the range of 0°C to 200 e C, or from 0°C to 160°C, and a pressure in the range of 0.1 to 100 atmospheres, or from 0.1 to 50 atmospheres, with some embodiments.
- the reaction is also typically performed in less than 24 hours, such as between 1 and 8 hours.
- the LRPEU compound can be added in less than a stoichiometric amount, it is typically added in at least a stoichiometric amount relative to the moles of terminal halogen present in the polymer. When added in excess of a stoichiometric amount, the LRPEU compound is typically present in an amount of no greater than 5 mole percent, such as 1 to 3 mole percent, in excess of the total moles of terminal halogen, with some embodiments.
- LRPEU compounds are described in further detail at column 12, line 15 through column 13, line 18 of United States Patent No. 8,268,433 B1 , which disclosure is incorporated herein by reference.
- the LRPEU is free of halogen groups.
- LRPEU compounds include, but are not limited to, 1 , 1-dimefhyiethyiene, 1 , 1 -diphenyiethylene, Ssopropenyi acetate, alpha- methyl styrene, 1 , 1-dialkoxy olefin and mixtures thereof.
- Additional examples of LRPEU compounds include, but are not limited to, dimethyl itaconate and diisobutene (2 ,4,4-irimethyl-l -pentene).
- ethyienicaily unsaturated radically po!ymerizable monomer and similar terms includes, hut are not limited to, vinyl monomers, aiiyilc monomers, olefins and other ethyienica!iy unsaturated monomers thai are radically polymerizable,
- Classes of vinyl monomers from which each M of Formula (V) can he independentiy derived include, but are not limited to, (meth)acryiates, vinyl aromatic monomers, vinyl haiides, and vinyl esters of carboxyiic acids, each of which can, with some embodiments, optionally include one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups.
- the (meth)acryEates are selected from at least one of: alkyi (meth)acrylates having from 1 to 20 carbon atoms in the alky!
- alkyi group includes or Is substituted with one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups.
- alkyi (meih)acrylates having from 1 to 20 carbon atoms in the alkyi group examples include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acryiate, propyl (meth)acrylate, isopropyl (meth)acry!ate, butyl (meth)acry!ate, isobutyl (meth)acrylate, tert-butyi (rneth)acryiate, 2-ethyihexyi (meth)acrylate, iauryf (meth)acryfate, isobomyi (meth)acryiaie, cyclohexyl ⁇ meth)acryiate and 3,3,5-trimethylcyclohexyl ⁇ meth)acrylate, one or more of which can, with some embodiments, optionally include in the alkyi group thereof one or more functional groups selected from hydroxyl groups, thio
- oxirane functional monomers from which each M of Formula (V) can be derived include, but are not limited to, glycidyl (meih)acrylate, 3, 4-epoxy cyclohex l methyl (meth)acrylate, 2- ⁇ 3,4- epoxycyciohexyl)efhyl (meth)acry!ate and ally! glycidyl ether.
- oxirane functionality can be incorporated into the polymer by post- reaction, such as by preparing a hydroxyl functional precursor polymer and converting the precursor polymer to an oxirane functional polymer by reacting at least
- Examples of vinyl aromatic monomers from which each M of Formuia (V) can be independently derived include, but are not limited to, styrene, p- chloromethyistyrene, divinyi benzene, vinyl naphtha iene and divinyi naphthalene.
- Vinyl ha!ides from which each can be independently derived include, but are not limited to, vinyl chloride and vinylldene fluoride.
- Vinyl esters of carboxy!tc acids include, but are not limited to, vinyl acetate, vinyl butyraie, vinyl 3,4- dimethoxybenzoate and vinyl benzoate.
- olefin and like terms is meant unsaturated aliphatic hydrocarbons having one or more double bonds, such as obtained by cracking petroleum fractions.
- examples of olefins from which each M of Formula (V) can be independently dervied include, but are not limited to, propylene, 1-butene, 1 ,3- butadtene, isobutyiene and diisobutylene.
- allyllc monomer(s) monomers containing substituted and/or unsubstiiuted alSylic functionality, such as one or more radicals represented by the following Formuia (VII),
- R 1 is hydrogen, halogen or a Ci to C 4 alkyi group. With some embodiments, R 1 is hydrogen or methyl and consequently Formula (VII) represents an unsubstiiuted (meth)a!!yl radical.
- allyllc monomers include, but are not limited to; (meth)a!!yl alcohol; (meth)a!!yi ethers, such as methyl (meth)al!y! ether; ally! esters of carfooxy!ic acids, such as (rneth)ai!y! acetate, (meth)al!y! butyrate, (meth)a!lyt 3,4-dimethoxybenzoate and (meth)aiiy! benzoate,
- ethylenically unsaturated radically poiymerizable monomers from which each M of Formuia (V) can be independently derived include, but are not limited to: cyclic anhydrides, such as ma!eic anhydride, 1-cyc!opentene-1 ,2- dicarboxylic anhydride and itaconic anhydride; esters of acids that are unsaturated but do not have alpha, beta-ethyienic unsaturatson, such as methyl ester of undecy!enic acid; and d iesters of ethylenically unsaturated dibasic acids, such as diethyl ma!eate.
- cyclic anhydrides such as ma!eic anhydride, 1-cyc!opentene-1 ,2- dicarboxylic anhydride and itaconic anhydride
- the polymers of the present invention can, with some embodiments, have polymer architecture selected from linear polymers, branched polymers, hyperbrancbed polymers, star polymers, graft polymers and mixtures thereof.
- the form, or gross architecture, of the polymer can be controlied by the choice of initiator and monomers used in its preparation.
- Linear polymers can be prepared by using initiators, such as represented by Formulas ⁇ [) and (il), having one or two radically transferable groups.
- Branched polymers can be prepared by using branching monomers, such as monomers containing radically transferable groups or more than one ethylenicaliy unsaturated radically polyrneriza le group, such as 2 ⁇ (2 ⁇ bromopropionoxy)ethyl acrylate, p-ch!oromethylstyrene and diethyleneglycol bis(methacryiate). Hyperbrancbed polymers can be prepared by increasing the amount of branching monomer used.
- branching monomers such as monomers containing radically transferable groups or more than one ethylenicaliy unsaturated radically polyrneriza le group, such as 2 ⁇ (2 ⁇ bromopropionoxy)ethyl acrylate, p-ch!oromethylstyrene and diethyleneglycol bis(methacryiate).
- Hyperbrancbed polymers can be prepared by increasing the amount of branching monomer used.
- Star polymers can be prepared using initiators having three or more radically transferable groups, such as represented by Formulas ⁇ 1 ⁇ and (II).
- Star- polymers can be prepared by art-recognized core-arm or arm-core methods. In the core-arm method, the star polymer is ' repared by polymerizing monomers in the presence of the po!yfunctional initiator. Polymer chains, or arms, of similar composition and architecture grow out from the initiator core, in the core-arm method. With the arm-core method, the arms are prepared separately from the core and can optionally have different compositions, architecture, molecular weight and polydispersiiy indices (PDI's).
- PDI's polydispersiiy indices
- the arms can have different equivalent weights (such as different active hydrogen equivalent weights), and some can have no functionality. After the preparation of the arms, they are attached to the core by art-recognized methods, so as to result in the formation of a arm-core polymer.
- the polymers of the present invention prepared by controlled radical polymerization can have, with some embodiments, a functional equivalent weight of at least 100 grams/equivalent, or at least 200 grams/e uivalent.
- the functional equivalent weight of the polymer is, with some embodiments, iess than 10,000 grams/equivalent, or less than 5,000 grams/equivalent, or iess than 1 ,000 grams/equivalent.
- the functional equivalent weight of the polymers of the present invention prepared by controlled radical polymerization can range between any combination of these values, inclusive of the recited values, such as from 100 to 10,000 grams/equivalent, or from 200 to 5,000 grams/equivalent, or from 200 to 1 ,000 grams/equivalent, inclusive of the recited values.
- the functionality (or functional groups) of the polymer can, with some embodiments, be selected from hydroxy! groups, thiol groups, primary amine groups, secondary amine groups, and oxi ane groups.
- the number average molecular weight (Mn) of the polymers of the present invention prepared by conirolied radical polymerization is with some embodiments at least 250, or at least 500, or at least 1 ,000, or at least 2,000.
- the polymers of the present invention prepared by controlled radical polymerization also have, with some embodiments, an Mn of less than 16,000, or less than 10,000, or less than 5,000.
- the Mn of the polymers of the present Invention prepared by controlled radical polymerization can, with some embodiments, range between any combination of these values, inclusive of the recited values, such as from 250 to 16,000, or from 500 to 10,000, or from 1 ,000 to 8,000, or from 2,000 to 7,000, inclusive of the recited values.
- the controlled radical polymerization (CRP) catalyst such as the ATRP transition metal catalyst, and its associated ligand are, with some embodiments, separated or removed from the polymer.
- the CRP catalyst such as the ATRP catalyst is removed, with some embodiments, prior to conversion of a precursor polymer to a functional polymer. Removal of the ATRP catalyst is achieved, with some embodiments, using known methods, including, for example, adding a catalyst binding agent to the a mixture of the polymer, solvent and catalyst, followed by filtering. Examples of suitable catalyst binding agents include, but are not limited to, alumina, silica, clay or combinations thereof.
- a mixture of the polymer, solvent and ATRP catalyst can be passed through a bed of catalyst binding agent, with some embodiments.
- the ATRP catalyst can be oxidized in situ and retained in the polymer polymer.
- the polymers of the present invention can be prepared, with some embodiments, in the absence of solvent, such as by a bulk polymerization process. With some embodiments, the polymer is prepared in the presence of a solvent, such as water and/or an organic solvent.
- a solvent such as water and/or an organic solvent.
- Classes of useful organic solvents include, but are not limited to, esters of carboxyiic acids, ethers, cyclic ethers, C 5 -Ci 0 alkanes, C5- C e cycloalkanes, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amides, nitrites, sulfoxides, sulfones and mixtures thereof.
- Supercritical solvents such as CO z , C C 4 alkanes and fluorocarbons
- aromatic hydrocarbon solvents such as xylene
- mixed aromatic solvents such as those commercially available from Exxon Chemical America under the trademark SOLVESSO.
- z is at least 2; and the spirooxazine represented by Formula (I) includes at least one first radically transferable group, and at least one second radically transferrabie group, in which for the spirooxazine represented by formuia (!) at least one of R 1 independently for each n, and R 2 Independently for each p, independently comprise said first radically transferable group, and at least one of R 3 independently for each q, R , R 5 and R 6 independently comprise said second radically transferable group.
- the indenonapbtbopyran represented by Formula (II) includes at least one first radically transferable group, and at least one second radically transferrabie group, in which for the indenonapbthopyran represented by Formula (li) at least one of B and B' independently comprise said first radically transferable group, and at least one of R 7 Independently for each x, R 8 independently for each y, R s and R 1Q independently comprise said second radically transferable group.
- z is 2; and the spirooxazine represented by Formula ⁇ 1 ⁇ includes one first radically transferable group, and one second radically transferrabie group, In which for the spirooxazine represented by Formula (I) one R 2 comprises said first radically transferable group, and one R 3 comprises said second radically transferable group.
- the Indenonapbthopyran represented by Formula (il) includes one first radically transferable group, and one second radically transferrabie group, In which for the indenonapbthopyran represented by Formula (II) one of B and S' comprises said first radically transferable group, and one R 8 comprises said second radically transferable group,
- one or more groups of the spirooxazine represented b Formula (1), such as Ri, R 2 , R3, R , Rs, and/or R 6 include a group represented by Formula (ill), as described previously herein.
- one or more groups of the indenonapbthopyran represented by Formuia (II) such as R 7 , R 8 , R 9 , R 10l B, and/or B' in each case independently include the group represented by the Formula (III), as described previously herein.
- X of the group represented by Formuia (IIS) can, with some embodiments be a halo group, such as CI, Br, and I,
- Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can Independentl be a thermoplastic polymer or a curable polymer.
- the polymer is a curable polymer it has, with some embodiments, one or more functional groups thai are reactive with the (i) functional groups of another material, such as a crossiinking agent, and/or (ii) other functional groups on the same polymer,
- Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can independently be a thermoplastic polymer or a curable poiymer.
- the polymer prepared by controlled radical polymerization Is a curable poiyme it has, with some embodiments, one or more functional groups that are reactive with the (!) functional groups of another material, such as a crossiinking agent, and/or (si) other functional groups on the same polymer prepared by controlled radical polymerization.
- the poiymer prepared by controlled radical polymerization includes at least one first reactive group; and the poiymer composition further includes at least one crossiinking agent that includes at least two second reactive groups that are reactive with and form covalent bonds with the first reactive group(s) of the poiymer prepared by controlled radical polymerization.
- the polymer that is prepared by controlled radical polymerization, includes at least one active hydrogen group selected from hydroxy!, thiol, carboxylic acid, primary amine, and secondary amine; and the polymer compositio further includes at least one crossiinking agent that Includes at least two functional groups seiected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates, With some further embodiments, the crossiinking agent includes at least two functional groups selected from oxiranes, thiooxiranes, isocyanates, ihioisocyanates. The crossiinking agent, in accordance with some additional embodiments, includes at least two functional groups selected from oxiranes and isocyanates.
- the crossiinking agent includes a separate polymer according to the present invention that is prepared by controlled radical polymerization, which Includes at least two functional groups selected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.
- the crossiinking agent polymer can be prepared in accordance with the description provided previously herein, using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (II) as a controlled radical polymerization initiator.
- the crosslinking agent is prepared by controlled radical polymerization, but is not prepared using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (ii) as a controlled radical polymerization initiator. With some further embodiments, the crosslinking agent is not prepared by controlled radical polymerization.
- the polymers prepared by controlled radical polymerization include at least one, such as two or more, radically poiymerlzable ethylenicaliy unsaturated groups, such as, but not limited to, (meth)acry!oyi groups and a!lyiic groups.
- the polymer compositions of the present invention can be cured by exposure to actinic radiation in the presence of a suitable initiator, such as a photopolymerization initiator, and an optional crosslinking agent that has two or more radically polymerizable ethylenicaily unsaturated groups, in accordance with art- re cognized methods.
- a suitable initiator such as a photopolymerization initiator
- an optional crosslinking agent that has two or more radically polymerizable ethylenicaily unsaturated groups
- isocyanate functional materials from which the crosslinking agent can be selected include but are not limited to, toiuene-2,4-diisocyanate; toluene ⁇ 2.6-ditsocyanate; diphenyl methane ⁇ 4,4' ⁇
- diisocyanate diphenyl methane ⁇ 2,4' ⁇ diisocyanaie; para-phenylene diisocyanate;
- biphenyi diisocyanate S.S'-dimethyM ⁇ '-diphersylene diisocyanate; tetramethylene- 1 ,4-diisocyanate; hexamethy!ene-1 ,6-diisocyanate; 2,2,4-trimethyi hexane-1 ,6- diisocyanate; lysine methyl ester diisocyanate; bis(isocyanato ethyf)fumarate;
- isophorone diisocyanate ethylene diisocyanate; dodecane-1 ,12-diisocyanate;
- the poiyisocyanate crosslinking agent can, with some embodiments, be selected from polyisocyanates prepared from dimers and trimers of diisocyante monomers. Dimers and trimers of diisocyanate monomers can be prepared by art- recognized methods, such as described in U.S. Pat. No. 5,777,061 at column 3, line 44 through column 4, line 40. Dimers and trimers of the above recited diisocyanate monomers can contain linkages selected from the group consisting of isocyanurate, uretdione, biuret; aiiophanaie and com inatio s thereof.
- the ssocyanate functional crossiinking agent can also be selected from (i) polyisocyanaie functional polymer having at least two isocyanafe groups, (si) oligomeric polyisocyanaie functional adduci and mixtures thereof.
- the polyisocyanaie functional polymer and oligomenc polyisocyanaie functional adduci can each contain structural linkages selected from urethane, i.e., -NH-C(0 ⁇ -0-, thiourethane, i.e., -NH-C(0) ⁇ S-, urea, e.g., -NH-C ⁇ 0)-NH ⁇ , and combinations of these structural linkages.
- the pofyisocyanate polymer can be prepared, by art-recognized methods, from one or more monomers having at least two reactive hydrogen groups, such as thiol, hydroxy, primary amine and secondary amine groups, and one or more monomers having two or more isocyanafe groups.
- the molar equivalent rat o of reactive hydrogen groups to isocyanafe groups is selected such that the resulting polymer has the desired end groups, i.e., isocyanafe groups,
- the number average molecular weight ( n) of the polyisocyanaie-funciionai polymer is less than 20,000, such as from 1 ,000 and 10,000, with some embodiments.
- the polyisocyanaie functional polymer is a polyisocyanaie functional po!yurethane prepared from aliphatic diois and aliphatic dtisocyanates.
- the polyisocyanaie functional po!yurethane ma be prepared using relatively small amounts of monomers having three or more functional groups, such as triols and/or tiisocyanaies, to increase the functionality and branching of the polyurethane, in accordance with art-recognized methods,
- oligomeric polyisocyanaie functional adduci a material that is substantially free of polymeric chain extension.
- Oligomeric polyisocyanaie functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, such as trimeihylolpropane (T P), and an Isocyanafe monomer, such as 1-isocyanato-3,3,5- irimethyl-5-isocyanatomethyicyciohexane (!PDI), in a molar ratio of 1 :3, respectively.
- T P trimeihylolpropane
- Isocyanafe monomer such as 1-isocyanato-3,3,5- irimethyl-5-isocyanatomethyicyciohexane (!PDI
- TMP-31PDI an oligomeric adduci having an average isocyanafe functionality of 3 can be prepared ("TMP-31PDI" ⁇ .
- the oligomeric polyisocyanaie functional adduct can contain structural linkages selected from the urethane, ihiourethane, urea and combinations thereof, as described previously herein.
- the active hydrogen group containing compound is aliphatic with some embodiments, such as T P, trishydroxyisocyanurate, peniaerythrito! and trlmethylolpropane tris(mereaptoacetate).
- the isocyanate monomer is, with some embodiments, a diisocyanate monomer and can be selected from those described previously herein,
- the isocyanate groups of the isocyanate functional crossiinki rig agent can, with some embodiments, be capped or blocked with a capping / blocking agent. After exposure to elevated temperature, the capping / blocking agent separates from the isocyanate functional material, allowing the free / unblocked Isocyanate groups thereof to react and form covalent bonds with the active hydrogen groups of the polymer prepared by controlled radical polymerization according to the present invention. After unblocking or decapping from the polyisocyanate, the capping agent can voiatrze out of the composition ⁇ prior to the composition becoming vitrified) and/or remain in the composition, such as a pjasticizer. With some embodiments, it is desirable that the capping agent not form bubbles in the composition and/or overly plasticize the composition after decapping.
- the capping groups of the capped polyisocyanate crosslinking agent ca be selected from, with some embodiments hydroxy functional compounds, 1 H- azoles, lactams, ketoximes and mixtures thereof.
- Classes of hydroxy functional compounds include, but are not limited to, aliphatic, cycioa!iphatic, or aromatic aikyi monoaicohois or phenolics.
- Specific examples of hydroxy functional compounds useful as capping agents include, but are not limited to: lower aliphatic alcohols such as methanol, ethanoi, and rv-butanol; cycloaliphatic alcohols such as cyc!ohexano!
- the hydroxy functional capping groups include the phenolics, examples of which include, but are not limited to, phenol itself and substituted phenols, such as cresol, nitrophenof and p-hydroxy methyl enzoate.
- Examples of i H-azoies that are useful as capping groups include, but are not limited to IH-imidazole, I H-pyrazoie, 1 H-3,5 ⁇ dimethyl pyrazole, 1 H ⁇ 2.5 ⁇ dimethyi pyrazole, 1 H-1 ,2,3-triazole, 1 H-1 ,2,3-benzotriazole, 1 H-1 ,2,4-triazole, 1 H-5-methyi- 1 ,2,4-triazole, and 1 H-3-amrno-1 ,2,4-triazole.
- Kefoximes useful as capping groups include those prepared from aliphatic or cycloaiip atic ketones.
- ketoxime capping groups include, but are limited to, 2-propanone oxime (acetone oxime), 2-fautanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-meihyl-2-butanone oxime, 4-methyi-2-penianone oxime, 3,3-dimethyi-2-buianone oxime, 2-heptanone oxime, 3-heptanone oxime, 4- heptanone oxime, 5-methyi-3- heptanone oxime, 2,6-dime ⁇ ftyi-4-heptartone oxime, eyclopentanone oxime, cydohexanone oxime, 3-methylcyclobexanone oxime, 3,3,5- trimethyicyclohexanone oxime and 3,5,5-trimethyl-2-cydohexene-5-one oxime.
- lactam capping groups include, but are not limited to, e- caproiaciam and 2-pyro!idinone.
- Other suitable capping groups include, morphoiine, 3-aminopropyi morphoiine and -hydroxy phthaiimide.
- Oxirane functional crosslinking agents can be prepared by reacting a hydroxy! functional material having at least two hydroxy! groups with a
- 2-(haiomethyl)oxirane such as 2-(chioromethyl)oxirane, which Is also referred to as epiehiorohydnn.
- polyois that can be used to prepare oxirane functional crosslinking agents include, but are not limited to, glycerin, trimethylolpropane, trirnethylolethane, irishydroxyethylisocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimetbyiene glycol, butanedioi, hepianedioi, hexanediol, octanedioi, 4,4' ⁇ propene-2 !
- 2-diyl)dicyclohexanoi 4,4'-methyienedicyclohexanol, neopentyi glycol, 2,2,3-frimethyipentane-l ,3-diol, 1 ,4-dimethyiolcyclohexane, 2,2,4- thmeihyipentane dioi, 4 ! 4'-(propane-2,2-diyl)diphenol ( and 4 i 4'-methyienediphenoL
- the oxirane functional crosslinking agent can be a polymeric material.
- the polymeric oxirane functional crosslinking agent can be prepared from an oxirane functional material having at least two oxirane groups and an active hydrogen functional material having at least two active hydrogen groups, such as at least two hydroxy! groups.
- Examples of polyois that can be used to prepare polymeric oxirane functional crosslinking agents include, but are not limited to those classes and examples recited previously herein with regard to preparing the oxirane functional crosslinking agent.
- the polymer prepared by controlled radical polymerization is present in the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 10 percent by weight, or at least 20 percent by weight, or at least 30 percent by weight, or at least 50 percent by weight, or at least 70 percent by weight, or at least 80 percent by weight, based on total weight of resin solids of the polymer composition.
- the polymer composition also, with some embodiments, contains the polymer prepared by controlled radical polymerization in an amount of less than or equal to 98 percent by weight, or less than or equal to 95 by weight, or less than or equal to 90 percent by weight, based on total weight of resin solids of the polymer composition.
- the polymer prepared by controlled radical polymerization can, with some embodiments, be present in the polymer composition of the present invention in an amount ranging between any combination of these values, inclusive of the recited values, such as from 2 to 98 percent by weight, or from 10 to 98 percent by weight, or from 20 to 98 percent by weight, or from 30 to 98 percent by weight, or from 50 to 98 percent by weight, or from 70 to 95 percent by weight, or from 80 to 90 percent by weight, in each case based on total weight of resin solids of the polymer composition.
- the polymer prepared by controlled radical polymerization is present in the polymer composition of the present invention in an amount of from 20 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 25 percent by weight, in each case based on total weight of resin solids of the polymer composition.
- the cross!inking agent is present, with some embodiments, In the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 5 percent by weight, or at least 10 percent by weight, based on total weight of resin solids of the polymer composition.
- the crosslinking agent can also, with some embodiments be present in the polymer composition in an amount of less than or equal to 70 percent by weight, or an amount of less than or equal to 50 percent by weight, or less than or equal to 30 percent by weight, or less than or equal to 20 percent by weight, based on total weight of resin solids of the polymer composition.
- the crosslinking agent can be present in the polymer composition of the present invention in an amount ranging between an combination of these values, inclusive of the recited values, such as from 2 to 70 percent by weight, or from 2 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 20 percent by weight, based on total weight of resin soiids of the curable particulate composition, and , inclusive of the recited values.
- the polymer prepared by controlled radical polymerization is present in the polymer composition, with some embodiments, in an amount of from 30 to 98 percent by weight, based on total resin solids weight of the polymer composition; and the crosslinking agent is present in the polymer composition, with some embodiments, in an amount of from 2 to 70 percent by weight, based on total resin solids weight of the polymer composition.
- the polymer compositions of the present invention include one or more additional polymers that do not include ⁇ and are free of) a residue of a mechanochramic compound, such as represented by Formulas (i) and (II), which can be referred to as non-mechanochromic polymers.
- nors-mechanochromic polymers include, but are not limited to, polyester polymers, po!yurethane polymers, polycarbonate polymers, poiyether polymers, pofyamide polymers, polyimide polymers, polyamideimide polymers, poiyurea polymers, poiysulfone polymers, poiyketone polymers, polyvinyl polymers, po!yolefins, poly(meth)acrylates, and combinations of two or more thereof.
- Each non-mechanochromic polymer can include, with some embodiments: one or more (such as two or more) active hydrogen groups, such as hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine; and/or one or more (such as two or more) functional groups that are reactive with active hydrogen groups, such as, cyclic carboxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxyiic acid esters, cyclic amides, and cyclic carbonates.
- active hydrogen groups such as hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine
- functional groups that are reactive with active hydrogen groups such as, cyclic carboxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxyiic acid esters, cyclic amides, and cycl
- the non-mechanochromic polymer is present in an amount of from 2 to 98 percent by weight, or from 10 to 80 percent by weight, or from 20 to 70 percent by weight, or from 30 to 60 percent by weight, or from 30 to 50 percent by weight, where the percent by weights are in each case based on the total weight of the polymer of the present invention (which includes a residue of a mechanochromic compound such as represented b Formulas (! and (I!)) and the non-mechanochromic polymer.
- the equivalent ratio of active hydrogen equivalents of the polymer prepared by controlled radical polymerization, to isocyanate or oxirane equivalents of the crossiinklng agent is, with some embodiments, from 0.7: 1 to 2:1 , or from 0.8:1 to 1,3:1.
- the polymer composition o the present Invention can be cured by any suitable methods.
- the polymer composition is thermosetting, and is curable by exposure to elevated temperature.
- cured is meant a three dimensional crosslink network formed by covending bond formation, such as between the active hydrogen groups of the polymer prepared by controlled radical polymerization and the isocyanate or oxirane groups of the crossiinklng agent.
- the temperature at which the thermosetting polymer composition of the present invention is cured is variable and depends in part on the amount of time during which curing Is conducted.
- thermosetting po ymer composition is cured at a temperature within the range of 90°C to 204°C, or from 149°C to 204°C, or from 154°C to 177°C. for a period of 20 to 80 minutes.
- the polymer compositions of the present invention can also, with some embodiments, include pigments and fillers.
- pigments include, but are not limited to: inorganic pigments, such as titanium dioxide and iron oxides; organic pigments, such as phthalocyanines, anthraquinones, quinacridones and thioindigos; and carbon blacks.
- fillers include, but are not limited to: silica, such as precipitated silicas; clay; and barium sulfate.
- pigments and fillers can, with some embodiments, be present in amounts of from 0,1 percent to 70 percent by weight, based on the total solids weight of the polymer composition (excluding solvent).
- the polymer compositions of the present invention can, with some embodiments, optionall contain additives such as, but not limited to: waxes for flow and wetting; flow control agents, such as poiy ⁇ 2 ⁇ ethyihexyl)acryla?e; antioxidants; and ultraviolet (UV) light absorbers.
- additives such as, but not limited to: waxes for flow and wetting; flow control agents, such as poiy ⁇ 2 ⁇ ethyihexyl)acryla?e; antioxidants; and ultraviolet (UV) light absorbers.
- useful antioxidants and UV light absorbers include, but are not limited to, those available commercially from BASF under the trademarks !RGANOX and TiNUVSN.
- These optional additives, when used, can be present In amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
- the polymer compositions of the present can, with some embodiments, include solvents, selected from water, organic solvents, and combinations thereof.
- Classes of organic solvents that can be present in the polymer compositions of the present invention include , but are not limited to: alcohols, e.g., methanol, ethanol, n-propano!, iso-propanol, n-butanoi, sec-butyl alcohol, fert-butyl alcohol, iso-butyi alcohol, furfuryi alcohol and tetrabydrofurfuryi alcohol; ketones or ketoalconois, e.g., acetone, methyl ethyl ketone, and diaceione alcohol; ethers, e.g., dimethyl ether and methyl ethyl ether; cyclic ethers, e.g., tetrahydrofuran and dioxane; esters, e.g., ethyl acetate., ethyl lactate, ethylene carbonate and propylene carbonate; poiyhydric alcohols, e.g.,
- Selles(s) can be present in the polymer compositions of the present invention, in an amount of at least 5 percent by weight, or at least 15 percent by weight, or at least 30 percent by weight, based on the total weight of the polymer composition.
- the sives(s) can also be present in the polymer composition In an amount of less than 95 percent by weight, or less than 80 percent by weight, or less than 60 percent by weight, based on the total weight of the pigment dispersion.
- the amount of solvent present in the polymer composition can range between any combination of these values, inclusive of the recited values, with some embodiments, such as from 5 to 95 percent by weight, or from 15 to 80 percent by weight, or from 30 to 60 percent by weight, in each case based on the total weight of the polymer composition,
- the polymer composition Includes an additive selected from heat stabilizers, light stabilizers, and combinations thereof.
- useful heat stabilizers and light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGA OX and TJNUVIN.
- the optional heat stabilizers and light stabilizers, when used, can be present in amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
- the present invention also relates to mechanochromic articles that include the polymer composition of the present invention as described previously herein.
- the mechanochromic article is selected from films, sheets, and 3-dimens!onai articles.
- the 3-dimensionai articles from which the mechanochromic articles of the present invention can be selected include, but are not limited to, ophthalmic articles, display articles, windows, mirrors, protective articles and support articles.
- the mechanochromic articles of the present invention are selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses.
- ophthalmic means pertaining to or associated with the eye and vision.
- Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but no!
- bifocal lenses bifocal lenses, trifocal lenses and progressive lenses
- other elements used to correct, protect, or enhance (cosmetically or otherwise) vision including without limitation, contact lenses, intra-ocular lenses, magnifying lenses, and protective lenses or visors.
- the mechanochromic articles of the present invention are selected from display articles, and the display articles are selected from screens, monitors, and security elements.
- display means the visible or machine-readable representation of information In words, numbers, symbols, designs or drawings.
- Non-limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
- the mechanochromic articles of the present invention are selected from protective articles, and the protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings.
- protective lenses include, but are not limited to, safety glasses and safety goggles, such as used in a laboratory and/or a work shop, such as a metal shop, welding shop, wood-working shop, automotive shop/garage, and the like.
- protective visors include, but are not limited to, those used with racing helmets (such as automotive, motorcycle, and boat racing helmets), aircraft helmets, hockey helmets, metal working helmets, and helmets used by ground military personnel.
- protective headgear include, but are not limited to, motorcycle helmets, aircraft helmets, speed boat helmets, automotive race helmets, baseball helmets, hockey helmets, equestrian helmets, helmets used by ground military personnel, construction helmets, oil filed helmets, and helmets used by metal workers.
- protective housings include, but are not limited to, housings for sensitive equipment, such as, analytical equipment, guidance systems (such as missile guidance systems), and medical equipment (such as insulin pumps),
- the mechanochromic articles of the present invention are, with some embodiments, selected from support articles, and the support articles are selected from rods, beams, crossarms, and combinations thereof.
- the rods, beams, and crossarms can be substantially unitary articles, or composed of a plurality of components, in which at least some of the components are the mechanochromic articles of the present invention.
- the mechanochromic article of the present invention is selected from a 3-dimensionai article, and the 3 ⁇ dimenslonsal article includes a layer residing over at least a portion of at least one surface of the 3-dsmensiona! article, in which the layer includes the polymer composition of the present invention as described previously herein, and is a mechanochromic layer.
- the mechanochromic layer can be selected from fiims, sheets, and/or coatings.
- the mechanochromic article of the present, invention is selected from a 3-dimenstona! article, and the 3-dimensionsal article includes a coating residing over at least a portion of at least one surface of the 3-dimensfona! article, in which the coating includes the polymer composition of the present invention as described previously herein, and is a mechanochromic coating.
- the coating is the polymer composition of the present invention, and the coating is a mechanochromic coating.
- the coating can be a single layer coating or a multiple layer coating, In which each layer thereof can have the same or a different composition.
- the coating is a multiple layer coating that includes a primer over at least a portion of a surface of the 3-dimensionai article, a mechanochromic layer formed over the primer layer (in which the mechanochromic layer Includes the polymer composition of the present invention), and an optional clear layer formed over the mechanochromic layer.
- the mechanochromic layer can be pigmented or unpigmented, with some embodiments.
- the optional clear layer which resides over the mechanochromic layer, can include an additive selected from heat stabilizers and/or light stabilizers.
- the heat stabilizers and light stabilizers can be present in amounf(s) and the thickness of the clear layer can be selected such that photochromic activation of the residue of the controlled radical polymerization initiator ⁇ represented by Formula (I) and/or (II), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantially eliminated.
- the heat stabilizers and light stabilizers can be present in the clear layer in a total amount of up to 40% by weight, based on the total solids weight of the dear layer.
- a mechanochromic article that includes the polymer composition of the present invention, in which the mechanochromic article further includes a coating residing over at least a portion of at least one surface of the mechanochromic article.
- the coating is free of the polymer composition of the present invention, and the coating includes an additive selected from heat stabilizers, Sight stabilizers, and combinations thereof.
- the coating residing over the mechanochromic article can be referred to as an overcoating.
- the overcoating, which resides over the mechanochromic article can be a clear overcoating, with some embodiments of the present invention.
- the heat stabilizers and light stabilizers can be present in amount(s) and the thickness of the clear overcoating can be selected such that photoch.ro mi c activation of the residue of the controlled radical polymerization initiator (represented by Formula (i) and/or (!l), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantiall eliminated.
- the heat stabilizers and light stabilizers can be present In the clear overcoating In a total amount of up to 40% by weight, based on the total solids weight of the clear overcoat,
- Part 1 describes the synthesis of controlled radical polymerization initiators
- Part 2 describes the preparation of polymers made by controlled radical polymerization using the initiators of Part 1.
- frlethylamine (1.1 Sg ) was added dropwise. The resulting dark solution was reffuxed for 1 hour, then cooled to room temperature and a blue product was collected via filtration. This was immediately placed into a Nitrogen-flushed 2oz jar. To the jar was added i !eihyiamine (2.88g), and dichloromethane (8.5 ml). This mixture was cooled in a dry ice/ethanol bath, and a solution of 2-bromoisobutyry! bromide (3.94g) In dichloromethane (1.5 mL) was added. The jar was reseaied and allowed to warm to room temperature. After stirring for 2 hours, the residue was dry packed onto a 6 inch by % inch silica plug and eluted with 500 mL of a 2: 1 solution of
- indeno[2 : ,3 ! :3,4]naphtho:[1 ,2-b]pyran (0.1g) was placed into a Nitrogen-flushed 25 mL round bottomed flask. To the flask was added dichioromethane (1.5g), then the mixture was cooled In an ice water bath. Triethylamine (0.0647g) was added, followed by 2-bromoisobutyryl bromide (0.08%,). The flask was allowed to warm to room temperature. After stirring overnight, the solvent was removed and the residue was redisso!ved in diethyl ether. The salts were removed via filtration, and the e!uent was concentrated.
- the mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed.
- the material was dissolved in teirahydroiuran (THF, 20.7g) and stirred open to the atmosphere for 5 minutes, at which time the viscous solution was filtered.
- the polymer was purified by precipitation into methanol. The off-white polymer was collected and dried under vacuum. The resulting polymeric compound was found to be reversibly photochromic under UV irradiation.
- Example 2 1 ,3,3-trimethy!spiro[indo!ine-2,3'-naphiho[2, 1 -b][1 ,4]oxazine3-5,5'-diyi bis(2-bromo-2- methyipropionate) of Example 2 (0.5g, 1 equiv), Cu metal (0.029g, 2 equivs), tris(2 ⁇ dimethylaminoethyijamsne (0,79 g, 2 equivs), and dry butyl acetate (1.3 mL). The resulting mixture was purged with dry Nitrogen for 20 min.
- Methyl acryiate (0.73, 37 equiv) and hydroxypropyl acryiate (0,96g, 33 equiv) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed. The material was dissolved in THF (20.7g) then filtered through a plug of glass wool. To the filtrate was added
- Example 3 4]nap tho 1 ,2-bJpyran of Example 3 (0.030Sg) was subjected to the conditions described in Example 8 except that 0.008g Cu, 0.029g tris(2- dimethylaminoethyi)amine, 4.32g of methyl acryjate, and 2.8g of D SO was used.
- Gel Permeation Chromatography in THF indicated a peak MW of 128,614 (theory 140,000) relative to a linear polystyrene standard,
- the initiator 1 ,3,3-frimethylspiroj;!ndoilne-2,3 , -naphtho(2,1-b] 1 ,4]oxazlne]-5 5 -diyi bis(2-bromo-2-melhylpropionate ⁇ of Example 2 (24.4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0094g Cu, 0.034g tris ⁇ 2-dimethyiaminoethyl)amine, 5.19g of methyl acryiate, and 3.4g of DMSO was used.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
L'invention concerne des initiateurs de polymérisation radicalaire contrôlée qui contiennent au moins un groupe transférable radicalement. Les initiateurs de polymérisation radicalaire contrôlée contiennent au moins l'un des éléments suivants : (a) un composé espiroxazine de formule (I), et (b) un indénonaphthopyran de formule (II) ; un ou plusieurs de R1, R2, R3, R4, R5 et R6 de l'espiroxazine, et un ou plusieurs de R7, R8, R9, R10, B et B' incluant indépendamment le groupe transférable radicalement. L'invention concerne également des polymères, par exemple des polymères mécanochromiques, qui sont préparés à partir de ces initiateurs de polymérisation radicalaire contrôlée, des compositions polymères qui incluent ces polymères, et des articles mécanochromiques qui incluent ces compositions polymères.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/833,828 | 2013-03-15 | ||
US13/833,828 US8889807B2 (en) | 2012-04-16 | 2013-03-15 | Controlled radical polymerization initiators |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014151543A1 true WO2014151543A1 (fr) | 2014-09-25 |
Family
ID=50631018
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/025960 WO2014151543A1 (fr) | 2013-03-15 | 2014-03-13 | Initiateurs de polymérisation radicalaire contrôlée |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2014151543A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11963868B2 (en) | 2020-06-01 | 2024-04-23 | Ast Products, Inc. | Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof |
EP4198102A4 (fr) * | 2020-12-24 | 2024-04-24 | Hoya Lens Thailand Ltd | Composé photochromique, composition photochromique, article photochromique et lunettes |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5645767A (en) | 1994-11-03 | 1997-07-08 | Transitions Optical, Inc. | Photochromic indeno-fused naphthopyrans |
US5763548A (en) | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
US5777061A (en) | 1996-02-14 | 1998-07-07 | Bayer Corporation | Blocked polyisocyanate crosslinkers for providing improved flow properties to coating compositions |
US5789487A (en) | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
US5807937A (en) | 1995-11-15 | 1998-09-15 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties |
US6019914A (en) | 1997-05-06 | 2000-02-01 | Essilor International Compagnie Generale D'optique | Photochromic spirooxazine compounds, their use in the field of ophthalmic optics |
US6113814A (en) | 1998-09-11 | 2000-09-05 | Transitions Optical, Inc. | Polymerizable polyalkoxylated naphthopyrans |
US6265489B1 (en) | 1998-08-31 | 2001-07-24 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing carboxylic acid functional polymers prepared by atom transfer radical polymerization |
US6268433B1 (en) | 1998-08-31 | 2001-07-31 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing epoxy functional polymers prepared by atom transfer radical polymerization |
US6296785B1 (en) | 1999-09-17 | 2001-10-02 | Ppg Industries Ohio, Inc. | Indeno-fused photochromic naphthopyrans |
US6555028B2 (en) | 1998-09-11 | 2003-04-29 | Transitions Optical, Inc. | Polymeric matrix compatibilized naphthopyrans |
EP1810982A1 (fr) * | 2004-11-09 | 2007-07-25 | Tokuyama Corporation | Formule durcissable par polymérisation |
US20090093601A1 (en) * | 2004-09-02 | 2009-04-09 | Polymers Australia Pty Limited | Photochromic Compounds Comprising Polymeric Substituents And Methods For Preparation And Use Thereof |
US7527754B2 (en) | 2005-12-21 | 2009-05-05 | Transitions Optical, Inc. | Photochromic indeno-fused naphthopyrans |
WO2013158379A1 (fr) * | 2012-04-16 | 2013-10-24 | Ppg Industries Ohio, Inc. | Composition de revêtement mécanochrome |
-
2014
- 2014-03-13 WO PCT/US2014/025960 patent/WO2014151543A1/fr active Application Filing
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5645767A (en) | 1994-11-03 | 1997-07-08 | Transitions Optical, Inc. | Photochromic indeno-fused naphthopyrans |
US5763548A (en) | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
US6887962B2 (en) | 1995-11-15 | 2005-05-03 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co)polymers having useful structures and properties |
US5807937A (en) | 1995-11-15 | 1998-09-15 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties |
US7572874B2 (en) | 1995-11-15 | 2009-08-11 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co)polymers having useful structures and properties |
US6538091B1 (en) | 1995-11-15 | 2003-03-25 | Carnegie Mellon University | Atom or group transfer radical polymerization |
US5777061A (en) | 1996-02-14 | 1998-07-07 | Bayer Corporation | Blocked polyisocyanate crosslinkers for providing improved flow properties to coating compositions |
US5789487A (en) | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
US6019914A (en) | 1997-05-06 | 2000-02-01 | Essilor International Compagnie Generale D'optique | Photochromic spirooxazine compounds, their use in the field of ophthalmic optics |
US6265489B1 (en) | 1998-08-31 | 2001-07-24 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing carboxylic acid functional polymers prepared by atom transfer radical polymerization |
US6268433B1 (en) | 1998-08-31 | 2001-07-31 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing epoxy functional polymers prepared by atom transfer radical polymerization |
US6113814A (en) | 1998-09-11 | 2000-09-05 | Transitions Optical, Inc. | Polymerizable polyalkoxylated naphthopyrans |
US6555028B2 (en) | 1998-09-11 | 2003-04-29 | Transitions Optical, Inc. | Polymeric matrix compatibilized naphthopyrans |
US6296785B1 (en) | 1999-09-17 | 2001-10-02 | Ppg Industries Ohio, Inc. | Indeno-fused photochromic naphthopyrans |
US20090093601A1 (en) * | 2004-09-02 | 2009-04-09 | Polymers Australia Pty Limited | Photochromic Compounds Comprising Polymeric Substituents And Methods For Preparation And Use Thereof |
EP1810982A1 (fr) * | 2004-11-09 | 2007-07-25 | Tokuyama Corporation | Formule durcissable par polymérisation |
US7527754B2 (en) | 2005-12-21 | 2009-05-05 | Transitions Optical, Inc. | Photochromic indeno-fused naphthopyrans |
WO2013158379A1 (fr) * | 2012-04-16 | 2013-10-24 | Ppg Industries Ohio, Inc. | Composition de revêtement mécanochrome |
Non-Patent Citations (1)
Title |
---|
DOUGLAS A DAVIS ET AL: "Force-induced activation of covalent bonds in mechanoresponsive polymeric materials", NATURE, NATURE PUBLISHING GROUP, UNITED KINGDOM, vol. 459, 7 May 2009 (2009-05-07), pages 68 - 72, XP002711320, ISSN: 0028-0836, DOI: DOI:10.1038/NATURE07970 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11963868B2 (en) | 2020-06-01 | 2024-04-23 | Ast Products, Inc. | Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof |
EP4198102A4 (fr) * | 2020-12-24 | 2024-04-24 | Hoya Lens Thailand Ltd | Composé photochromique, composition photochromique, article photochromique et lunettes |
EP4198583A4 (fr) * | 2020-12-24 | 2024-05-29 | Hoya Lens Thailand Ltd | Composition photochromique, article photochromique et lunettes |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2019202232B2 (en) | Photochromic articles that include photochromic-dichroic materials | |
US6153126A (en) | Photochromic six-membered heterocyclilc-fused naphthopyrans | |
AU730870B2 (en) | Novel water soluble photochromic compounds | |
CA2256479C (fr) | Nouveaux indenonaphtopyranes fusionnes heterocycliques photochromiques | |
US5514817A (en) | Substituted phenanthropyrans | |
JP2505357B2 (ja) | ホトクロミックナフトピラン | |
EP2651914B1 (fr) | Composés et compositions photochromes | |
AU2011341557A1 (en) | Photochromic compounds and compositions | |
AU2011344179A1 (en) | Photochromic compounds and compositions | |
WO2012170287A1 (fr) | Articles photochromiques polarisants | |
US8889807B2 (en) | Controlled radical polymerization initiators | |
JP2003513098A (ja) | 5、6位に複素環を持つナフトピラン、その調製並びにそれらを含有する組成物およびマトリクス | |
WO2014151543A1 (fr) | Initiateurs de polymérisation radicalaire contrôlée | |
US6608215B2 (en) | Oxygen-containing heterocyclic fused naphthopyrans | |
WO2014152259A1 (fr) | Compositions de polymères contenant des polymères mécano-chromiques | |
EP3268375B1 (fr) | Composés thiénochromène photochromiques | |
WO2013090220A1 (fr) | Naphtopyranes indéno-condensés ayant des groupes à insaturation éthylénique | |
KR102473969B1 (ko) | 실롤 및 게르몰 융합된 고리 광변색성 화합물 | |
WO2018206096A1 (fr) | Composés de phénanthréopyrane indéno-fusionnés photochromiques | |
KR20140014107A (ko) | 광변색성 화합물 및 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14721074 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14721074 Country of ref document: EP Kind code of ref document: A1 |