EP3420006A1 - Composition polymérisable de faible viscosité précurseur de matériaux renforcés à l'impact - Google Patents
Composition polymérisable de faible viscosité précurseur de matériaux renforcés à l'impactInfo
- Publication number
- EP3420006A1 EP3420006A1 EP17710604.4A EP17710604A EP3420006A1 EP 3420006 A1 EP3420006 A1 EP 3420006A1 EP 17710604 A EP17710604 A EP 17710604A EP 3420006 A1 EP3420006 A1 EP 3420006A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- radical
- composition according
- nitroxide
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000010146 3D printing Methods 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000002966 varnish Substances 0.000 claims abstract description 4
- -1 1-phenyl-2-methylpropyl Chemical group 0.000 claims description 49
- 150000003254 radicals Chemical class 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920003232 aliphatic polyester Polymers 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001002 functional polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920001400 block copolymer Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 125000005262 alkoxyamine group Chemical group 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- AHIHJODVQGBOND-UHFFFAOYSA-M propan-2-yl carbonate Chemical compound CC(C)OC([O-])=O AHIHJODVQGBOND-UHFFFAOYSA-M 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 102220043986 rs116134953 Human genes 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- HBAIZGPCSAAFSU-UHFFFAOYSA-N 1-(2-hydroxyethyl)imidazolidin-2-one Chemical compound OCCN1CCNC1=O HBAIZGPCSAAFSU-UHFFFAOYSA-N 0.000 description 1
- YPAURZBMECSUPE-UHFFFAOYSA-N 1-(2-hydroxyethyl)imidazolidin-2-one;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCN1CCNC1=O YPAURZBMECSUPE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- PFPUZMSQZJFLBK-UHFFFAOYSA-N 2-(2-oxoimidazolidin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCNC1=O PFPUZMSQZJFLBK-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FAKVHJPTDNJHKJ-UHFFFAOYSA-N 2-aminoprop-2-enoic acid prop-2-enoic acid Chemical class C(C=C)(=O)O.NC(C(=O)O)=C FAKVHJPTDNJHKJ-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- FKLBRTJRFNSRJD-UHFFFAOYSA-N 2-methyl-6-trimethylsilylhex-1-en-3-one Chemical compound CC(=C)C(=O)CCC[Si](C)(C)C FKLBRTJRFNSRJD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08F222/10—Esters
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
Definitions
- the present invention relates to a low viscosity precursor polymerizable composition of impact-reinforced materials.
- Such a composition is useful in areas such as adhesives, varnishes and coatings, fabric impregnating resins or woven materials, in flexible substrate coatings or in 3D printing processes.
- the composition may be polymerized using a photoinitiator under the influence of electromagnetic radiation (gamma, UV, visible, infrared) from a source such as a lamp capable of generating such radiation ( lasers, plasma arc lamps, xenon lamps, mercury lamps, halogen lamps or light-emitting diode lamps).
- a source such as a lamp capable of generating such radiation ( lasers, plasma arc lamps, xenon lamps, mercury lamps, halogen lamps or light-emitting diode lamps).
- a multi-photonic emitter source can be used.
- the composition may also be polymerized using a radical initiator.
- compositions which have good mechanical properties at the end of the polymerization and which, during application, ie before polymerization, have a low viscosity are sought.
- compositions by heart-bark particles.
- polyerized compositions have a level of resistance to crack propagation and insufficient impact when seeking compositions which have low viscosity typically less than 10 Pa.S.
- this approach requires preparing these particles separately which complicates the manufacture of these compositions.
- the invention relates to a polymerizable composition
- a polymerizable composition comprising a mixture of at least one monomer capable of radically polymerizing and having at least one polymerizable function, at least one dormant polymeric flexible sequence capable of generating at least one radical, and at least one generator. free radicals.
- the monomers capable of radical polymerization they may be multifunctional monomers or not chosen from vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomers chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes in particular alpha-methylstyrene, silylated styrenes, acrylic monomers such as acrylic acid or its salts, alkyl acrylates, cycloalkyl acrylates or aryl acrylates, such as methyl acrylate or ethyl acrylate; , butyl, ethylhexyl or phenyl, isobornyl, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy acrylates, and the like.
- vinylaromatic monomers such as styrene or substituted sty
- - or aryloxy-polyalkylene glycol such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, acrylates methoxy-polyethylene glycol-polypropylene glycol or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate ( MAM), lauryl, cyclohexyl, allyl, phenyl or naphthyl, isoborn
- 1,3-butylene glycol, 1,4-butylene glycol, polyfunctional methacrylic monomers such as polyol polymethacrylates, alkylene glycol polymethacrylates or allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol , from
- the monomers capable of radical polymerization may also be polymeric or oligomeric sequences capable of radically polymerizing in addition to one or more monomers listed above.
- Polymeric or oligomeric sequences capable of radical polymerization are understood to mean polymeric or oligomeric sequences having any Tg (glass transition temperature) as measured by DSC (differential thermal analysis), but preferably greater than 0 ° C. and even more preferably greater than 0 ° C. 50 ° C and having at least one double bond.
- Polyoxyethylene or polyoxypropylene is also called polyethylene glycol or polypropylene glycol;
- polyesters derived from the esterification with acrylic or methacrylic acid of a polyester polyol or monool.
- the said polyesters are polycondensation products between a polyacid (diacid) and a polyol (diol) and may be of variable structure depending on the structures of these polyacid components and / or polyols.
- polyurethanes acrylates or methacrylates that may result from the esterification reaction of a polyurethane polyol or monool (of polyester type for example) with acrylic or methacrylic acid or reaction between a polyurethane prepolymer (oligomer)
- epoxy acrylate oligomers resulting from the acrylation or methacrylation of a mono or polyepoxidized oligomer for example epoxidized oligodienes such as epoxidized polybutadiene or epoxidized polyunsaturated oils.
- Acrylic or methacrylated acrylic oligomers such as copolymers of glycidyl methacrylate (MAGLY) with another acrylic or methacrylic comonomer, by reaction with acrylic or methacrylic acid.
- MAGLY glycidyl methacrylate
- These sequences have a weight-average molecular mass of between 200 and 10,000 g / mol and preferably between 300 and 2,000 g / mol, as measured by steric exclusion chromatography (polystyrene standards).
- the dormant polymeric flexible sequences capable of generating at least one radical exhibit a Tg (glass transition temperature) measured by DSC (differential thermal analysis) below 0 ° C. and preferably below -20 ° C.
- the soft sequences comprise butyl acrylate.
- the flexible sequences are present within the composition in mass proportions between 0.1 and 50%, preferably between 0.1 and 30%, more preferably between 0.1 and 15%, and more preferably between 0.1 and 7% and more particularly between 0.1 and 5%, ideally between 2 and 5%. At 3.5% it is highlighted a singular point where the resistance to the impact goes through a maximum.
- dormant polymeric soft sequences are prepared by controlled radical polymerization such as NMP ("Nitroxide Mediated Polymerization"), RAFT ("Reversible Addition and Fragmentation Transfer”), ATRP ("Atom Transfer Radical Polymerization”), INIFERTER ("Initiator-Transfer- Termination "), RITP (" Reverse Iodine Transfer
- ITP Iodine Transfer Polymerization
- dormant or dormant chain sequence in English is explained in the book “the chemistry of radical polymerization” by Graeme Moad and David H. Solomon, Elsevier 2006, page 456. In particular, they are capable of generating at least a radical which can then initiate a polymerization on said sequence.
- the dormant polymeric flexible sequences are prepared by radical polymerization controlled by nitroxides, and more particularly nitroxides from alkoxyamines derived from the stable free radical (1).
- the dormant polymeric soft sequences in this case are therefore alkoxyamines: (1)
- the radical R 1 has a molar mass greater than 15.034 g / mol.
- the radical R 1 can be a halogen atom such as chlorine, bromine or iodine, a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group such as an alkyl or phenyl radical, or an ester - COOR or an alkoxyl group -OR, or a phosphonate group -PO (OR) 2 > as long as it has a molar mass greater than 15.0342.
- the monovalent radical R- ⁇ is said in position ⁇ with respect to the nitrogen atom of the nitroxide radical.
- the remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are connected to each other via a divalent radical, so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals.
- the radical R 1 has a molar mass greater than 30 g / mol.
- the radical R 1 may, for example, have a molar mass of between 40 and 450 g / mol.
- the radical R 1 may be a radical comprising a phosphoryl group, said radical R 1 may be represented by the formula: R 1
- R and R which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms.
- R and / or R may also be a halogen atom such as a chlorine or bromine atom or a fluorine or iodine atom.
- the radical R 1 may also comprise at least one aromatic ring as for the phenyl radical or the naphthyl radical, the latter may be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
- alkoxyamines derived from the following stable radicals are preferred:
- alkoxyamines used in controlled radical polymerization must allow good control of the sequence of monomers. Thus they do not all allow good control of certain monomers.
- the alkoxyamines derived from TEMPO make it possible to control only a limited number of monomers, the same goes for the alkoxyamines derived from 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide. (TIPNO).
- alkoxyamines derived from nitroxides corresponding to formula (1) particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tert-butyl-1-diethylphosphono-2, 2-dimethylpropyl. nitroxide allow to expand to a large number of monomer controlled radical polymerization of these monomers.
- the dormant polymeric flexible sequences are therefore polyalkoxyamines and can be represented by the formula Z (-T) n in which Z denotes the flexible segment, T is a nitroxide and n is an integer greater than or equal to 1, and preferably between 2 and 4 terminals included. According to a still preferred form, n is equal to 3.
- Such flexible polyalkoxyamine pendant sequences can be prepared by reacting the monomers of the flexible sequence with precursors, themselves polyalkoxyamines and described in EP1526138.
- the polymerization reaction of the composition is initiated with the aid of a free radical resulting from the decomposition of an initiator or a photoinitiator.
- a free radical resulting from the decomposition of an initiator or a photoinitiator acts of a radical resulting from the decomposition of a radical initiator either by temperature, or by a redox reaction, or other redox system that can generate radicals, for example the methylene bis (diethyl) pair. malonate) - cerium IV, or the couple H 2 02 / Fe 2+ .
- radical initiator it may be chosen from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals and azo compounds.
- Suitable radical initiators are, for example, isopropyl carbonate, benzoyl peroxide, lauroyl, caproyl, dicumyl, tert-butyl perbenzoate, tert-butyl 2-ethyl perhexanoate, cumyl hydroperoxide, l, 1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, t-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate.
- radical initiators selected from the above list.
- the preferred radical initiator is a peroxide, and more particularly benzoyl peroxide.
- the radical is generated by the reaction between a peroxide and an amine.
- any type of amine capable of reacting with a peroxide may be used.
- DMPT dimethyl-p-toluidine
- HMDA p-hydroxymethyl-N, N-dimethyl aniline
- NDMA p-nitro-N, N-dimethyl aniline
- DMAB p-dimethylamino benzaldehyde
- the radical is derived from the decomposition of a photoinitiator.
- Photoinitiators are compounds that can generate free radicals when these compounds are exposed to electromagnetic radiation.
- the electromagnetic radiations have wavelengths in the ultraviolet or visible range, but it is not beyond the scope of the invention to use wavelengths in shorter wavelength ranges ( X-rays, or gamma) or longer (infra-red see beyond).
- It may also be a photoinitiator capable of generating free radicals by absorption at least two photons.
- photoinitiators can be of any type. Preferably, they are chosen from those which generate the free radicals by a homolytic cleavage reaction in position a relative to the carbonyl group, such as the ether derivatives.
- benzoines hydroxyalkylphenones, dialkoxyacetophenones, as well as derivatives of acylphosphine oxides, and in the ⁇ -position such as ketone sulphides and derivatives of sulfonyl ketones, those which form free radicals by the removal of hydrogen from a hydrogen donor.
- benzophenones or thioxanthones The process involves a charge transfer complex with an amine, followed by electron and proton transfer to form an initiator alkyl radical and an inactive cetyl radical.
- photoinitiators or a combination of photoinitiators and radical initiator (s) whose radicals are generated thermally or by a reaction of oxido-reduction, for example methylene bis (diethyl malonate) - cerium IV or the pair 3 ⁇ 402 / Fe 2+ .
- initiators used in combination with photoinitiators are diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals and azo compounds.
- Suitable radical initiators are, for example, isopropyl carbonate, benzoyl peroxide, lauroyl, caproyl, dicumyl, tert-butyl perbenzoate, tert-butyl 2-ethyl perhexanoate, cumyl hydroperoxide and the like.
- compositions of the invention may also comprise various additives, such as plasticizers, thermal stabilizers or UV stabilizers, mercaptans, sulphites, bisulphites, thiosulfites, hydroxylamines, amines, hydrazine (N 2 H 4 ), phenylhydrazine (PhNHN3 ⁇ 4), hydrazones, hydroquinone, flavonoids, beta carotene, vitamin A, tocopherols, vitamin E, propyl or octyl gallate, BHT, propionic acid, ascorbic acid , sorbates, reducing sugars, sugars comprising aldehydes, glucose, lactose, fructose, dextrose, potassium tartrate, nitrites, dextrin, aldehydes, glycine, antioxidants, dyes , fillers or short or long organic or mineral fibers depending on the end use of the object obtained by using the composition of the invention.
- additives such as plastic
- compositions of the invention are thus preferably used in 3D-lithographic printing (SLA) processes (digital light processing (DLP, "polyjet” technology and 2PP (using 2-photon polymerization).
- SLA 3D-lithographic printing
- compositions of the invention can also be used in the field of adhesives, coextrusion binders, varnishes and coatings, impregnating resins for fabrics or woven materials, short or long fibers, whether or not they are mineral, printing on flexible media (paper, polymer, metal).
- the compositions are usable in a range of
- the invention also relates to the polymerized compositions in object form as well as the objects thus obtained.
- Example 1 Synthesis of a Flexible Trifunctional Polyalkoxyamine Butyl Polyacrylate Suspension Block (PAbu)
- 1 liter glass reactor equipped with a propeller stirrer is introduced into a double jacket for heating by circulation of oil.
- reaction mixture After introduction of the reagents, the reaction mixture is heated (temperature setpoint on the oil circulating in the jacket: 90 ° C.). The temperature of the reaction mixture reaches 80 ° C in about 30 minutes.
- the temperature of the reactor is maintained at 80 ° C. for 240 min.
- the resulting reaction mixture is introduced by suction into a jacketed stainless steel reactor, the ethanol solvent is then removed by evaporation at 55 ° C under reduced pressure for 2 hours.
- 126 g of a trialkoxylamine are thus recovered, the yield is quantitative.
- a 738.6 g of butyl acrylate and 9.626 g of trialkoxyamine are introduced into a 2-liter metal reactor equipped with a propeller stirrer, a double jacket of heating by circulation of oil and a vacuum / nitrogen plug.
- the reaction mixture is degassed three times under vacuum / nitrogen.
- the reactor is then closed and stirring (100 rpm) and heating (temperature setpoint on the oil flowing in the jacket 125 ° C) are started.
- the temperature of the reaction mixture reaches 113 ° C. in about 30 minutes.
- the pressure is around 1.5 bar.
- the reactor temperature is maintained at 115 ° C for 510 min.
- the excess butyl acrylate is then removed by evaporation at 80 ° C under reduced pressure for 2 hours.
- block copolymers are prepared according to the protocol described in EP1526138 and are also available commercially (Nanostrength M52N ® and D51N, from Arkema).
- the first block copolymer (BCP 2, M52N) is a polymethyl methacrylate-butyl polyacrylate-polymethyl methacrylate (PMMA-PABu-PMMA) copolymer with a weight-average molecular weight of 140 Kg / mole, measured by SEC (polystyrene standards).
- the second block copolymer (BCP 1, D51N) is a copolymer polymethyl methacrylate-butyl polyacrylate (PMMA-PABu) with a molecular weight of 62 Kg / mole measured by SEC (polystyrene standards).
- the monomers capable of polymerizing are mixed in darkness either with PABu or with the block copolymer together until dissolution, then the photoinitiator is added.
- the resulting mixture is then poured into a mold consisting of 2 glass panes separated by a PVC seal which is then irradiated in a UV oven (Delolux 03S mercury UV lamp) for 60 seconds.
- Specimens type 1 according to the standard NF EN ISO 179-1 (February 2001) are made by cutting after demolding of the polymerized composition:
- Table 1 summarizes the different types of compositions used in the context of the invention and outside the invention (comparative tests), the values of the constituents are given in% by mass, as well as the measured values of their viscosity, rheological behavior and resistance to corrosion. impact after polymerization:
- the impact resistance is measured according to standard NF EN ISO 179-1 (February 2001); Charpy shock not cut.
- the viscosity of the formulations is determined on an imposed stress rheometer type MCR301 from ANTON PAAR.
- the measurement is performed by flow stress sweep at 20 ° C.
- the geometry used is of the duvet type for which the temperature regulation is ensured by the Peltier effect.
- the quilt geometry used is given in FIG.
- the formulation without photoinitiator is introduced into the air gap of the comet geometry. using a disposable pipette.
- the range of shear gradient varies in logarithmic mode from 0.1 to 1000 s -1 with a measurement of 10 points per decade.
- Test 23 Control 18 7 65 7 10 1 25 8 Test 24 18 7 65 7 10 1 3 55 13
- the formulations of the invention all have a low viscosity but all exhibit an increase in impact resistance compared to the references and in the presence of a large variety of polar monomers (SR 256, SR259 or SR531 - Tests 13 to 18) or apolar (SR 313 - Tests 19 and 20) acrylates or methacrylates (SR 313 and HPMA - Tests 19 and 20) of high functionality (CN2305, hyperbranched acrylate - Tests 25 and 26) or low functionality (SR 420, monofunctional acrylates - Tests 25 to 28), as well as in the presence of various chemical functions such as hydroxyls (HPMA - Test 19 and 20 or CN104 - Tests 23 and 24), urethane functions (CN9900) or simple esters (CN2505 - Tests 27 and 28).
- polar monomers SR 256, SR259 or SR531 - Tests 13 to 18
- SR 313 - Tests 19 and 20 acrylates or meth
Abstract
Description
Claims
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FR1651491A FR3047991B1 (fr) | 2016-02-24 | 2016-02-24 | Composition polymerisable de faible viscosite precurseur de materiaux renforces a l'impact |
PCT/FR2017/050398 WO2017144819A1 (fr) | 2016-02-24 | 2017-02-23 | Composition polymérisable de faible viscosité précurseur de matériaux renforcés à l'impact |
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EP3420006A1 true EP3420006A1 (fr) | 2019-01-02 |
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US (1) | US20190085113A1 (fr) |
EP (1) | EP3420006A1 (fr) |
JP (1) | JP6751769B2 (fr) |
CN (1) | CN108699200B (fr) |
CA (1) | CA3013936C (fr) |
FR (1) | FR3047991B1 (fr) |
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WO (1) | WO2017144819A1 (fr) |
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FR3040707B1 (fr) * | 2015-09-04 | 2019-08-30 | Arkema France | Composition adhesive photopolymerisable |
DK3428199T3 (da) * | 2017-07-12 | 2020-10-19 | Arkema France | Strålingshærdelig belægningssammensætning til forbedring af overfladeegenskaberne af plast |
CN109971252A (zh) * | 2019-02-26 | 2019-07-05 | 传美讯电子科技(珠海)有限公司 | 一种uv喷墨墨水及其制备方法 |
US11767381B2 (en) * | 2021-09-29 | 2023-09-26 | Snf Group | 2-dimethylaminoethyl acrylate polymers and their preparation method |
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FR2730240A1 (fr) * | 1995-02-07 | 1996-08-09 | Atochem Elf Sa | Stabilisation d'un polymere par un radical libre stable |
KR100551524B1 (ko) * | 2002-01-22 | 2006-02-13 | 아르끄마 | 니트록사이드 존재하에 조절된 라디칼 중합에 의해 수득된 블락 코폴리머를 함유하며 충격 강화된 물질의 제조 및 사용 방법 |
FR2861394B1 (fr) * | 2003-10-24 | 2006-01-20 | Arkema | Procede de preparation de polyalcoaxymines utilisables comme amorceurs pour la polymerisation radicalaire de (co)polymeres vivants polyfonctionnels |
WO2007124911A1 (fr) * | 2006-05-01 | 2007-11-08 | Dsm Ip Assets B.V. | Composition de résine durcissable par rayonnement et procédé d'imagerie tridimensionnelle rapide utilisant celle-ci |
CN102869692B (zh) * | 2010-05-03 | 2014-09-17 | 阿克马法国公司 | Uv能固化的密封剂 |
FR2969633B1 (fr) * | 2010-12-23 | 2015-02-06 | Arkema France | Composition pour des plaques coulees nanostructurees reticulees |
ES2534975T3 (es) * | 2011-05-12 | 2015-04-30 | Dow Global Technologies Llc | Proceso de polimerización de estabilizador y proceso para la preparación de polioles poliméricos |
JP6388119B2 (ja) * | 2014-09-19 | 2018-09-12 | 東洋インキScホールディングス株式会社 | 活性エネルギー線重合性樹脂組成物、及びそれを用いてなる積層体 |
US9587062B2 (en) * | 2014-12-15 | 2017-03-07 | Henkel IP & Holding GmbH and Henkel AG & Co. KGaA | Photocrosslinkable block copolymers for hot-melt adhesives |
FR3030526B1 (fr) * | 2014-12-18 | 2018-06-15 | Arkema France | Polymerisation radicalaire d'alcoxyamines a basse temperature |
US10131735B2 (en) * | 2014-12-18 | 2018-11-20 | Arkema France | Low-temperature radical polymerisation of alkoxyamines |
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2016
- 2016-02-24 FR FR1651491A patent/FR3047991B1/fr active Active
-
2017
- 2017-02-23 CN CN201780013401.2A patent/CN108699200B/zh active Active
- 2017-02-23 WO PCT/FR2017/050398 patent/WO2017144819A1/fr active Application Filing
- 2017-02-23 JP JP2018544190A patent/JP6751769B2/ja active Active
- 2017-02-23 CA CA3013936A patent/CA3013936C/fr active Active
- 2017-02-23 EP EP17710604.4A patent/EP3420006A1/fr active Pending
- 2017-02-23 US US16/078,981 patent/US20190085113A1/en not_active Abandoned
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2018
- 2018-08-15 IL IL261168A patent/IL261168B/en unknown
Also Published As
Publication number | Publication date |
---|---|
JP6751769B2 (ja) | 2020-09-09 |
IL261168B (en) | 2022-03-01 |
CN108699200B (zh) | 2021-09-21 |
CA3013936A1 (fr) | 2017-08-31 |
FR3047991A1 (fr) | 2017-08-25 |
JP2019506513A (ja) | 2019-03-07 |
WO2017144819A1 (fr) | 2017-08-31 |
CN108699200A (zh) | 2018-10-23 |
IL261168A (en) | 2018-10-31 |
FR3047991B1 (fr) | 2020-03-20 |
US20190085113A1 (en) | 2019-03-21 |
CA3013936C (fr) | 2020-12-15 |
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