WO2020114983A1 - Sels métalliques éthyléniquement insaturés à base de zirconium et de lanthane - Google Patents
Sels métalliques éthyléniquement insaturés à base de zirconium et de lanthane Download PDFInfo
- Publication number
- WO2020114983A1 WO2020114983A1 PCT/EP2019/083357 EP2019083357W WO2020114983A1 WO 2020114983 A1 WO2020114983 A1 WO 2020114983A1 EP 2019083357 W EP2019083357 W EP 2019083357W WO 2020114983 A1 WO2020114983 A1 WO 2020114983A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylate
- salt
- ethylenically unsaturated
- mono
- Prior art date
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- 150000003839 salts Chemical class 0.000 title claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 title abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000003085 diluting agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010146 3D printing Methods 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 76
- 239000000243 solution Substances 0.000 claims description 30
- -1 cycloaliphatic Chemical group 0.000 claims description 25
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 22
- 239000002609 medium Substances 0.000 claims description 22
- 229920002601 oligoester Polymers 0.000 claims description 21
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000002051 biphasic effect Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 150000004000 hexols Chemical class 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 3
- 150000002603 lanthanum Chemical class 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- WQINSVOOIJDOLJ-UHFFFAOYSA-N 2-(1,3-dioxoisoindol-2-yl)acetic acid Chemical compound C1=CC=C2C(=O)N(CC(=O)O)C(=O)C2=C1 WQINSVOOIJDOLJ-UHFFFAOYSA-N 0.000 claims description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 claims description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical class OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920005628 alkoxylated polyol Polymers 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical class C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010908 decantation Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 2
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010894 electron beam technology Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 2
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- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 2
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- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 claims description 2
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- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims 1
- GRKHFCJIWXNKDK-UHFFFAOYSA-N C=1(C(C(=O)O)=CC=CC1)C=1C(C(=O)O)=CC=CC1.C=1(C(CC=CC1)(C(=O)O)C(=O)O)C1=CC=CC=C1 Chemical compound C=1(C(C(=O)O)=CC=CC1)C=1C(C(=O)O)=CC=CC1.C=1(C(CC=CC1)(C(=O)O)C(=O)O)C1=CC=CC=C1 GRKHFCJIWXNKDK-UHFFFAOYSA-N 0.000 claims 1
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- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BXQPCGFPJPDYMZ-UHFFFAOYSA-N OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O BXQPCGFPJPDYMZ-UHFFFAOYSA-N 0.000 description 1
- KCJHIMJJWZQEJY-UHFFFAOYSA-N OC(C1=CC=CC=C1C(OCC1OC1)=O)=O.OC(C1=CC=CC=C1C(OC1=CC=CC=C1)=O)=O Chemical compound OC(C1=CC=CC=C1C(OCC1OC1)=O)=O.OC(C1=CC=CC=C1C(OC1=CC=CC=C1)=O)=O KCJHIMJJWZQEJY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical class CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VNXBKJFUJUWOCW-UHFFFAOYSA-N methylcyclopropane Chemical compound CC1CC1 VNXBKJFUJUWOCW-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/08—Allyl alcohol
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
Definitions
- the present invention relates to an ethylenically unsaturated and (co) polymerizable metal salt soluble in an ethylenically unsaturated reactive diluent, which is based on zirconium or lanthanum and an ethylenically unsaturated hemi-ester of a dicarboxylic acid, a process for the preparation of said salt, a crosslinkable composition comprising it and its various uses in materials for optical and dental applications, in composite materials, in molding compositions, in 3D printing compositions and for 3D articles, such as for coatings or adhesives and also relates to the resulting crosslinked finished product.
- Ethylenically unsaturated metal salts are already known and in particular zinc or calcium salts such as zinc di (meth) acrylates or calcium di (meth) acrylates used as crosslinking agents in elastomers as described in US 5,314,187 or US 5,506,308.
- WO 00/075241 and more particularly EP 1 980 565 and EP 1 189 994 describe the synthesis of soluble zinc salts, starting from Zn oxide (ZnO) and from hemi-ester / functionalized acid (meth) acrylate.
- the first step is the synthesis of the hemi-ester / acid by reaction of a cyclic anhydride with HE (M) A.
- the second step is a classic esterification reaction between the hemi-ester / acid and Zinc oxide, the water formed during the reaction is distilled to shift the equilibrium with an azeotropic solvent. When this reaction is complete, a (meth) acrylate monomer is added to the medium and then the solvent removed under reduced pressure.
- the described method of preparation is not sufficient to obtain other soluble metal salts, such as the salts of zirconium, zirconium or lanthanum.
- the ethylenically unsaturated soluble salts of Zinc described have limited functionality (2) and are insufficient for applications in even more efficient materials and in particular having a high refractive index and a high mechanical strength with thermal stability. high.
- the new ethylenically unsaturated and soluble and copolymerizable metal salts in an ethylenically unsaturated reactive diluent or in a crosslinkable composition containing it remedy the drawbacks and shortcomings of the metal salts known from the prior art with the additional advantages: wide spectrum of use in homogeneous and varied crosslinkable compositions with a wide range of targeted applications depending on the choice of components of said composition due to the performance of said metal salt and its solubility in said compositions.
- the first object of the invention relates to an ethylenically unsaturated (co) polymerizable metal salt, soluble in an ethylenically unsaturated reactive diluent, which salt is based on Zirconium or Lanthanum and on an ethylenically unsaturated hemi-ester specific for dicarboxylic acid.
- Said salt can be or be presented in the form of a homogeneous solution in at least one ethylenically unsaturated reactive diluent.
- Another subject of the invention relates to a first process for the preparation of said metal salt with recovery of said salt as such in the form of a salt by mass (100%).
- Another method of preparation in the form of a solution in at least one ethylenically unsaturated reactive diluent is another object of the invention.
- Another subject of the invention relates to a crosslinkable composition comprising at least one metal salt according to the invention.
- Two final objects of the invention relate respectively to the use of said metal salt according to the invention in crosslinkable compositions and also to the resulting crosslinked object.
- the first object of the present invention relates to an ethylenically unsaturated (co) polymerizable metal salt which is soluble in an ethylenically unsaturated reactive diluent, which salt is a zirconium or zirconium oxide salt or a lanthanum salt with a hemi- ethylenically unsaturated ester of a dicarboxylic acid of formula (I): (X) n -Rl-C> 2C-R- C0 2 H and optionally in addition to said hemi-ester (I), in the presence (or there is presence) of a saturated carboxylic monoacid of formula (II): R2CO2H and said salt is defined according to one of the following formulas (III), (IV) or (V):
- R being the residue without the carboxy groups, of a dicarboxylic acid of aliphatic, cycloaliphatic, aromatic or mixed structure
- said dicarboxylic acid R (- ⁇ 2H) 2 is selected from: for aliphatic diacids: maleic, fumaric, succinic, itaconic, dioic butane, dioic pentane, dioic hexane, dioic heptane, dioic octane, dioic nonane, dioic decane, dioecan dodecane dimers of C36 fatty acids or among their mixtures, preferably among: maleic acid, succinic acid and itaconic acid for cycloaliphatic diacids: cyclohexane acid 1,4-, 1,3- or -1,2-dicarboxylic, tetrahydrophthalic acid, norbornane dicarboxylic acids or their mixtures for aromatic diacids: ortho-, iso- or terephthalic acid, tetrabromo phthalic acid, naphthalene
- X being allyl: allyl alcohol, monoether of allyl alcohol with a C 2 to C 36 aliphatic diol which may be alkoxylated or an oligoether diol or an oligoester diol, allyl alcohol diether with an aliphatic triol which may be alkoxylated or a triol oligoether or triol oligoester, triether of allyl alcohol-with an aliphatic tetrol which may be alkoxylated or with a tetrol oligoether or oligoester, mono-, di- or tri-allyl ester derivatives of a dicarboxylic acid hemi-ester / allyl alcohol with a polyol of respective OH functional groups of 2, 3 and 4, preferably from: allyl alcohol and monoether of allyl alcohol with a C 2 to C 36 aliphatic diol which can be alkoxylated for X being vinyl: vinyl alcohol, vinyl alcohol monoether with a
- said dicarboxylic acid of residue R is selected from aromatic dicarboxylic acids. More particularly, said diacid is iso- and terephthalic acid and biphenyl-2,2'dicarboxylic acid.
- said group X is a (meth) acrylate group and said monoalcohol HO-Rl- (X) n is selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy pentyl (meth ) acrylate, hydroxy hexyl (meth) acrylate, mono (meth) acrylate of diethylene glycol, mono (meth) acrylate of neopentyl glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of dipropylene glycol, mono (meth) tripropylene glycol acrylate, mono (meth) polyethylene glycol acrylate of Mn ⁇ 1000, mono (meth) polypropylene glycol acrylate of Mn ⁇ 1000, mono (meth) polytetramethylene glycol acrylate, hydroxylated polycaprolactone mono (
- x 0 for the salts of respective formulas (III), (IV) and (V) as defined above.
- R2C02- and its choice in the formulas of the metal salts according to the invention according to respective formulas (III), (IV) and (V) can cause the targeted properties of said metal salt to be adjusted and its affinity with the components of the crosslinkable composition targeted to adjust a particular performance in the desired desired application.
- R2 is therefore an important parameter of modular structure like the parameter x, both of which can be modulated according to the application needs and final performance targeted for the crosslinkable composition.
- Said metal salt according to the invention is more particularly in solution in at least one ethylenically unsaturated reactive diluent, in particular chosen from (meth) acrylic, vinyl or allyl monomers and their mixtures, more particularly with a functionality in ethylenically unsaturated groups ranging from 1 to 6.
- ethylenically unsaturated reactive diluent in particular chosen from (meth) acrylic, vinyl or allyl monomers and their mixtures, more particularly with a functionality in ethylenically unsaturated groups ranging from 1 to 6.
- the second object of the invention relates to a process for the preparation of said metal salt, which process comprises the following steps: i) Preparation of said ethylenically unsaturated hemi-ester of formula (I), and optionally of said saturated hemi-ester of formula (VI) ) by respective reactions:
- C 1 -C 3 alkyl acetates alkanes in particular hexane or heptane, cycloalkanes in particular cyclohexane, methylcyclohexane, methylcyclopropane, methylcyclobutane, aromatics in particular toluene, benzene, xylene, ethylbenzene , cumene, mesitylene and preferably from: ethyl acetate, heptane, cyclohexane, methylcyclohexane and toluene.
- Another subject of the invention relates to a crosslinkable composition, which comprises at least one metal salt as defined above or obtained by a process as defined above according to the invention.
- said composition is crosslinkable by peroxide route and / or by radiation route.
- said composition comprises, in addition to said salt, at least one reactive diluent copolymerizable with said salt, selected from mono- or multi-functional (meth) acrylic, vinyl or allyl monomers, preferably (meth) acrylic or vinyl monomers mono- or multi-functional.
- said reactive diluent copolymerizable with said salt is at least one (meth) acrylic monomer chosen from Ci-Cis (meth) acrylates optionally alkoxylated, hydroxy alkyl (meth) acrylates with C2-C 4 alkyl optionally alkoxylated, (meth) acrylate esters of alcohols of aromatic or cycloaliphatic structure, epoxy (meth) acrylates, urethane (meth) acrylates, multi- (meth) acrylic esters of aliphatic polyols, optionally alkoxylated polyols or of oligoether polyols having 2 to 4 ether units, with functionality ranging from 2 to 6.
- "Of aromatic or cycloaliphatic structure” means "comprising aromatic or cycloaliphatic groups”.
- said composition additionally comprises at least one ethylenically unsaturated oligomer carrying at least one ethylenically unsaturated group. More particularly, said oligomer carries from 1 to 6 ethylenically unsaturated groups chosen from: (meth) acrylate, vinyl and allyl, preferably (meth) acrylate or vinyl.
- said oligomer is selected from: vinyl esters, unsaturated polyesters, polyethers (meth) acrylates, polyesters (meth) acrylates, (meth) acrylic copolymers (meth) acrylates, epoxy (meth) acrylates, oligourethane (meth) acrylates, polycarbonate (meth) acrylates, polycarbonate urethane (meth) acrylates.
- said composition is crosslinkable by UV radiation with the presence of a photoinitiator or by electron beam without photoinitiator.
- Said crosslinkable composition is chosen in particular from: coating composition, adhesive composition, molding composition, composition of composite material reinforced with glass or carbon fibers, 3D printing composition.
- An object of the invention relates to the use of said metal salt in crosslinkable compositions.
- the use relates to materials with a high refractive index for optical applications, in particular for ophthalmic correction lenses, optical prisms or composite materials reinforced with fiberglass or carbon, materials for dental applications, compositions 3D printing, the manufacture of 3D objects and the promotion of adhesion of coatings or adhesives on polar substrates.
- the present invention also covers a crosslinked product, which results from the use of at least one metal salt as defined above or obtained by a process as defined above or from the crosslinking of a composition such as defined above according to the invention.
- said crosslinked product it is: a coating, an adhesive, a composite material, in particular with glass or carbon fiber reinforcement, a molded part, a correction lens or high refractive index optical prism, dental part, 3D printing or 3D article.
- Example 1 Zirconyl of HEA diphtalate diluted in biphenyl methanol acrylate (H008 from KPX)
- Step 1 In a 1 L reactor, add, with stirring and air bubbling (0.3 ml / H / kg), 29.71 g of hydroxyethyl acrylate (HEA, Mw 116.12 g / mol, Sigma Aldrich ), 37.89 g of phthalic anhydride (Mw 148.12, Sigma Aldrich) and 0.07 g of methyl hydroquinone ether (EMHQ, Aldrich). Heat and maintain at 100 ° C until the final stopping criterion determined by the measurement of the acid number (IA) expressed in mg KOH / g. The expected theoretical final AI value is 212.3 mg KOH / g.
- HOA hydroxyethyl acrylate
- EMHQ methyl hydroquinone ether
- Step 2 In the same reactor, at 60 ° C and under air bubbling, add in 30 minutes a solution of 21.29 g of sodium bicarbonate (NaH ⁇ 3, Mw 84.0 g / mol, Aldrich) dissolved in 70 g of demineralized water. A release of CO2 is observed. At the end of the addition of the sodium bicarbonate solution, the reaction medium is milky but becomes slightly homogeneous after 1 hour of stirring. The pH of the solution is measured at 7.
- sodium bicarbonate NaH ⁇ 3, Mw 84.0 g / mol, Aldrich
- Step 3 At 60 ° C., with stirring and with air bubbling, 500 g of ethyl acetate is added to the medium and then a solution of 48.19 g of zirconyl octahydrate dichloride (Zr0Ü 2 .8H20, Mw 322 , 25 g / mol, Alfa aesar) dissolved in 32.0 g of demineralized water is added over 15 minutes to the biphasic medium. As the addition takes place, a white precipitate forms in the medium which then dissolves in the organic phase. At the end of the addition, with the agitator stopped, two phases are observed, a clear colorless aqueous phase and an opaque white organic phase.
- Step 4 In a separating funnel, the aqueous phase is removed and the organic phase washed once with 50 g of a 20% sodium chloride solution.
- Step 5 After filtration on paper, 55 g of biphenyl methanol acrylate (H008, BPX) is added to the organic medium and then the ethyl acetate is evaporated under reduced pressure.
- biphenyl methanol acrylate H008, BPX
- the product obtained is a homogeneous liquid of 121.94 g, ie a final yield on the salt of zirconyl di-phthalate of HEA of 84%.
- the viscosity at 25 ° C of the mixture is 5400 mPa.s and with a refractive index of 1.591.
- Example 2 Zirconyl of HEMA diphthalate diluted in cumyl phenol acrylate (CD590 from Sartomer)
- Step 1 In a 1 L reactor, introduce with stirring and air bubbling (0.3 ml / H / kg ), 31.62 g of hydroxyethyl methacrylate (HEMA, Mw 130.14 g / mol, Sigma Aldrich), 35.98 g of phthalic anhydride (Mw 148.12, Sigma Aldrich) and 0.07 g of ether hydroquinone methyl (EMHQ, Aldrich). Heat and maintain at 100 ° C until the final stopping criterion determined by the measurement of the acid number (IA) expressed in mg KOH / g. The expected theoretical final AI value is 201.6 mg KOH / g.
- IA acid number
- Step 2 In the same reactor, at 60 ° C and under air bubbling, add in 30 minutes a solution of 21.75 g of sodium bicarbonate (NaH ⁇ 3, Mw 84.0 g / mol, Aldrich) dissolved in 70 g of demineralized water. A release of CO2 is observed. At the end of the addition of the sodium bicarbonate solution, the reaction medium is milky but becomes slightly homogeneous after 1 hour of stirring. The pH of the solution is measured at 7.
- sodium bicarbonate NaH ⁇ 3, Mw 84.0 g / mol, Aldrich
- Step 3 At 60 ° C., with stirring and with air bubbling, 500 g of ethyl acetate is added to the medium and then a solution of 49.22 g of zirconyl octahydrate dichloride (Zr0Ü 2 .8H20, Mw 322 , 25 g / mol, Alfa aesar) dissolved in 32.0 g of demineralized water is added over 15 minutes to the biphasic medium. As the addition takes place, a white precipitate forms in the medium which then dissolves in the organic phase. At the end of the addition, with the agitator stopped, two phases are observed, a clear colorless aqueous phase and an opaque white organic phase.
- Step 4 In a separating funnel, the aqueous phase is removed and the organic phase washed once with 50 g of a 20% sodium chloride solution.
- Step 5 After filtration on paper, 84.79 g of cumyl phenol acrylate (CD590, Sartomer) is added to the organic medium and then the ethyl acetate is evaporated under reduced pressure.
- CD590 cumyl phenol acrylate
- the product obtained is a homogeneous liquid of 155.72 g, ie a final yield on the salt of zirconyl di-phthalate of HEMA of approximately 88%.
- the viscosity at 25 ° C of the mixture is 4590 mPa.s and with a refractive index of 1.561.
- Example 3 Zirconyl of phenyl glycidyl diphthalate ether acrylate diluted in biphenyl methanol acrylate (H008 from KPX)
- Step 1 In a 1 L reactor, introduce with stirring and air bubbling (0.3 ml / H / kg), 44.32 g of phenyl glycidyl ether acrylate (CN131B, Mw 300 g / mol, Sartomer), 35.98 g of phthalic anhydride (Mw 148.12, Sigma Aldrich) and 0.07 g of ether hydroquinone methyl (EMHQ, Aldrich).
- Step 2 In the same reactor, at 60 ° C and under air bubbling, add in 30 minutes a solution of 15.38 g of sodium bicarbonate (NaH ⁇ 3, Mw 84.0 g / mol, Aldrich) dissolved in 70 g of demineralized water. A release of CO2 is observed. At the end of adding the bicarbonate solution of sodium, the reaction medium is milky but becomes slightly cloudy homogeneous after 1 hour of stirring. The pH of the solution is measured at 7.
- Step 3 At 60 ° C., with stirring and with air bubbling, a solution of 29.45 g of zirconyl octahydrate dichloride (Zr0Ü 2 .8H20, Mw 322.25 g / mol, Alfa aesar) dissolved in 25.0 g demineralized water is added over 15 minutes to the medium. A white precipitate forms very quickly.
- zirconyl octahydrate dichloride Zr0Ü 2 .8H20, Mw 322.25 g / mol, Alfa aesar
- Step 4 The white precipitate is isolated by filtration and then dried overnight in an oven at 100 ° C. The recovered product is then dissolved in 100 g of toluene. The cloudy solution is filtered on paper to obtain a clear and homogeneous filtrate.
- Step 5 After filtration on paper, 80.0 g of biphenyl methanol acrylate (H008 from KPX) is added to the organic medium and then the toluene is evaporated under reduced pressure.
- the product obtained is a slightly hazy homogeneous liquid of 132.0 g, ie a final yield on the zirconyl salt of phenyl glycidyl ether acrylate diphtalate of approximately 66%.
- the viscosity at 25 ° C of the mixture is 35,000 mPa.s and with a refractive index of 1.594.
- Example 4 Lanthanum of HEMA triphthalate diluted in biphenyl methanol acrylate (H 008 from KPX)
- Step 1 In a 1 L reactor, introduce, with stirring and air bubbling (0.3 ml / H / kg), 15.56 g of hydroxyethyl methacrylate (HEMA, Mw 130.14 g / mol, Sigma Aldrich ), 17.70 g of phthalic anhydride (Mw 148.12, Sigma Aldrich) and 0.035 g of methyl hydroquinone ether (EMHQ, Aldrich). Heat and maintain at 100 ° C until the final stopping criterion determined by the measurement of the acid number (IA) expressed in mg KOH / g. The expected theoretical final AI value is 201.6 mg KOH / g.
- HEMA hydroxyethyl methacrylate
- Mw 148.12 phthalic anhydride
- EMHQ methyl hydroquinone ether
- Step 2 In the same reactor, at 60 ° C and under air bubbling, add in 30 minutes a solution of 10.69 g of sodium bicarbonate (NaHCC> 3, Mw 84.0 g / mol, Aldrich) dissolved in 100 g of demineralized water. A release of CO2 is observed. At the end of the addition of the sodium bicarbonate solution, the reaction medium is milky but becomes slightly homogeneous after 1 hour of stirring. The pH of the solution is measured at 7.
- Step 3 At 60 ° C., with stirring and with air bubbling, 350 g of ethyl acetate is added to the medium and then a solution of 49.22 g of trichloride Lanthanum heptahydrate (LaÜ 3 .7H20, Mw 371.37 g / mol, Aldrich) dissolved in 50.0 g of demineralized water is added to the medium over 15 minutes biphasic. As the addition takes place, a white precipitate forms in the medium which then dissolves in the organic phase. At the end of the addition, with the agitator stopped, two phases are observed, a clear colorless aqueous phase and a slightly cloudy organic phase.
- Step 4 In a separating funnel, the aqueous phase is removed and the organic phase washed once with 50 g of a 10% sodium chloride solution.
- Step 5 After filtration on paper, 30 g of biphenyl methanol acrylate (H008 from KPX) is added to the organic medium and then the ethyl acetate is evaporated under reduced pressure.
- the product obtained is a homogeneous liquid of 65.8 g, ie a final yield on the lanthanum salt of HEMA triphthalate of approximately 91%.
- the viscosity at 25 ° C of the mixture is 9200 mPa.s and a refractive index of 1.588.
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP19809854.3A EP3891159A1 (fr) | 2018-12-03 | 2019-12-02 | Sels métalliques éthyléniquement insaturés à base de zirconium et de lanthane |
US17/299,030 US20220024844A1 (en) | 2018-12-03 | 2019-12-02 | Zirconium-based and lanthanum-based ethylenically unsaturated metal salts |
CN201980080252.0A CN113166175A (zh) | 2018-12-03 | 2019-12-02 | 基于锆和基于镧的烯属不饱和金属盐 |
KR1020217020678A KR20210098512A (ko) | 2018-12-03 | 2019-12-02 | 지르코늄-기반 및 란탄-기반, 에틸렌계 불포화 금속 염 |
JP2021531604A JP2022510003A (ja) | 2018-12-03 | 2019-12-02 | ジルコニウムに基づく及びランタンに基づくエチレン性不飽和金属塩 |
IL283648A IL283648A (en) | 2018-12-03 | 2021-06-02 | Ethylenically unsaturated metal salts based on zirconium and on lanthanum |
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FR1872212A FR3089223B1 (fr) | 2018-12-03 | 2018-12-03 | Sels métalliques éthyléniquement insaturés à base de zirconium et de lanthane |
FR1872212 | 2018-12-03 |
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US (1) | US20220024844A1 (fr) |
EP (1) | EP3891159A1 (fr) |
JP (1) | JP2022510003A (fr) |
KR (1) | KR20210098512A (fr) |
CN (1) | CN113166175A (fr) |
FR (1) | FR3089223B1 (fr) |
IL (1) | IL283648A (fr) |
TW (1) | TWI724666B (fr) |
WO (1) | WO2020114983A1 (fr) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5314187A (en) | 1991-07-26 | 1994-05-24 | Wilson Sporting Goods Co. | Golf ball with improved cover |
JPH0762279A (ja) * | 1993-08-25 | 1995-03-07 | Ajinomoto Co Inc | 塗料、インキ組成物 |
US5506308A (en) | 1995-04-11 | 1996-04-09 | Interface, Inc. | Precure retardation of free radical cured elastomers |
WO2000075241A2 (fr) | 1999-06-02 | 2000-12-14 | Sartomer Company, Inc. | Composes solubles dans l'huile et contenant des metaux, compositions et procedes associes |
US6703518B1 (en) * | 2003-03-05 | 2004-03-09 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Fluoride-releasing compositions |
US20150192851A1 (en) * | 2013-12-05 | 2015-07-09 | Tokyo Ohka Kogyo Co., Ltd. | Negative resist composition, method of forming resist pattern, and complex |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8414705D0 (en) * | 1984-06-08 | 1984-07-11 | Wiggins Teape Group Ltd | Coating substrates |
CN109983082B (zh) * | 2016-11-28 | 2021-11-02 | 阿科玛法国公司 | 可固化的组合物 |
-
2018
- 2018-12-03 FR FR1872212A patent/FR3089223B1/fr active Active
-
2019
- 2019-12-02 WO PCT/EP2019/083357 patent/WO2020114983A1/fr unknown
- 2019-12-02 US US17/299,030 patent/US20220024844A1/en active Pending
- 2019-12-02 KR KR1020217020678A patent/KR20210098512A/ko unknown
- 2019-12-02 CN CN201980080252.0A patent/CN113166175A/zh active Pending
- 2019-12-02 EP EP19809854.3A patent/EP3891159A1/fr active Pending
- 2019-12-02 JP JP2021531604A patent/JP2022510003A/ja active Pending
- 2019-12-03 TW TW108144134A patent/TWI724666B/zh active
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2021
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5314187A (en) | 1991-07-26 | 1994-05-24 | Wilson Sporting Goods Co. | Golf ball with improved cover |
JPH0762279A (ja) * | 1993-08-25 | 1995-03-07 | Ajinomoto Co Inc | 塗料、インキ組成物 |
US5506308A (en) | 1995-04-11 | 1996-04-09 | Interface, Inc. | Precure retardation of free radical cured elastomers |
WO2000075241A2 (fr) | 1999-06-02 | 2000-12-14 | Sartomer Company, Inc. | Composes solubles dans l'huile et contenant des metaux, compositions et procedes associes |
EP1189994A2 (fr) | 1999-06-02 | 2002-03-27 | Sartomer Company, Inc. | Composes solubles dans l'huile et contenant des metaux, compositions et procedes associes |
EP1980565A1 (fr) | 1999-06-02 | 2008-10-15 | Sartomer Company, Inc. | Composés solubles dans l'huile et contenant des métaux, compositions et procédés associés |
US6703518B1 (en) * | 2003-03-05 | 2004-03-09 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Fluoride-releasing compositions |
US20150192851A1 (en) * | 2013-12-05 | 2015-07-09 | Tokyo Ohka Kogyo Co., Ltd. | Negative resist composition, method of forming resist pattern, and complex |
Non-Patent Citations (1)
Title |
---|
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1995, XP002791933, retrieved from STB Database accession no. 1995:750565 * |
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Publication number | Publication date |
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FR3089223B1 (fr) | 2022-05-06 |
IL283648A (en) | 2021-07-29 |
US20220024844A1 (en) | 2022-01-27 |
TW202039515A (zh) | 2020-11-01 |
EP3891159A1 (fr) | 2021-10-13 |
KR20210098512A (ko) | 2021-08-10 |
CN113166175A (zh) | 2021-07-23 |
JP2022510003A (ja) | 2022-01-25 |
TWI724666B (zh) | 2021-04-11 |
FR3089223A1 (fr) | 2020-06-05 |
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